Δ1-pyrrolines used as pesticides

ABSTRACT

Novel Δ 1 -pyrrolines of the formula (I) 
                         
in which
     R 1 , R 2 , R 3 , A, R 4  and m have the meanings given in the description,
 
a number of processes for preparing these substances, and their use for controlling pests, and also novel intermediates and their preparation.

The present patent application has been filed under 35 U.S.C. 371 as anational stage application of PCT/EP02/09866, filed Sep. 4, 2002, whichwas published in German as International Patent Publication WO 03/024220on Mar. 27, 2003, which is entitled to the right of priority of GermanPatent Application 101 45 772.3, filed Sep. 17, 2001.

The present invention relates to novel Δ¹-pyrrolines, to a number ofprocesses for preparing them and to their use as pesticides.

It is already known that numerous Δ¹-pyrrolines possess insecticidalproperties (cf. WO 00/21958, WO 99/59968, WO 99/59967 and WO 98/22438).The activity of these substances is good, but still leaves something tobe desired in some cases.

This invention now provides novel Δ¹-pyrrolines of the formula (I)

in which

-   R¹ represents halogen or methyl,-   R² represents hydrogen or halogen,-   R³ represents —N(R⁶)—C(═Y)—X—R⁷,    and-   a) A represents arylene or 5-membered heteroarylene having 1 to 3    heteroatoms, containing 0 to 3 nitrogen atoms, 0 to 1 oxygen atom    and/or 0 to 1 sulphur atom, or 6-membered heteroarylene having 3    nitrogen atoms or 6-membered heteroarylene having 1 nitrogen atom    and 1 to 2 further heteroatoms, of which 0 to 2 may be oxygen atoms    and/or 0 to 2 may be sulphur atoms, each arylene or heteroarylene    being optionally substituted from one to four times by identical or    different substituents R⁵, and    -   Y represents O (oxygen) or S (sulphur), and    -   X represents O (oxygen), S (sulphur) or NR⁸,        or-   b) A represents pyridinylene, pyrimidinylene, pyrazinylene or    pyridazinylene each optionally substituted once or twice by    identical or different substituents R⁵, and    -   Y represents O (oxygen) or S (sulphur), and    -   X represents S (sulphur) or NR⁸,        or-   c) A represents pyridinylene, pyrimidinylene, pyrazinylene or    pyridazinylene each optionally substituted once or twice by    identical or different substituents R⁵, and    -   Y represents S (sulphur), and    -   X represents O (oxygen),        or-   d) A represents pyridinylene, pyrimidinylene, pyrazinylene or    pyridazinylene each optionally substituted once or twice by    identical or different substituents R⁵, and    -   Y represents O (oxygen), and    -   X represents O (oxygen),        and-   R⁴ and R⁵ independently of one another represent halogen, alkyl,    alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio,-   m represents 0, 1, 2, 3 or 4,-   R⁶ represents hydrogen or alkyl,-   R⁷ and R⁸ independently of one another represent hydrogen or    represent alkyl or alkenyl each optionally substituted one or more    times by identical or different substituents selected from the group    consisting of halogen, alkylcarbonyl, alkylcarbonyloxy, alkylamino,    dialkylamino, alkoxy, alkylthio, alkoxyalkoxy, haloalkoxy,    haloalkylthio and halogenalkoxyalkoxy;    -   or represent cycloalkyl, cycloalkylalkyl, aryl, arylalkyl,        saturated or unsaturated 5- to 10-membered heterocyclyl or        heterocyclylalkyl each of which is optionally substituted one or        more times by identical or different substitutents selected from        the group consisting of halogen, alkyl, haloalkyl, alkoxy,        haloalkoxy, alkylthio, haloalkylthio, alkylcarbonyl and        alkoxycarbonyl,-   R⁶ and R⁷ further together represent alkylene optionally substituted    one or more times by alkyl, or-   R⁷ and R⁸ further, together with the nitrogen atom to which they are    attached, represent a saturated or unsaturated 5- to 10-membered    heterocycle which may optionally contain a further heteroatom group    from the series —O—, —S— and —NR⁹— and which may optionally be    substituted one or more times by identical or different substituents    selected from the group consisting of halogen, alkyl, alkoxy,    alkylthio, haloalkyl, haloalkoxy and haloalkylthio, and-   R⁹ represents hydrogen, alkyl or alkenyl.

Where appropriate, depending on the nature and number of thesubstituents, the compounds of the formula (I) may be in the form ofgeometrical and/or optical isomers, regioisomers or configurationalisomers, or isomer mixtures thereof in varying compositions. The pureisomers and the isomer mixtures are claimed in accordance with theinvention.

It has also been found that Δ¹-pyrrolines of the formula (I) may beprepared by

-   A) reacting Δ¹-pyrrolines of the formula (II)

-    in which    -   R¹, R², R⁴ and m have the meanings given above and    -   Z¹ represents chlorine, bromine, iodine, —OSO₂CF₃ or        —OSO₂(CF₂)₃CF₃,        in a tandem reaction with (hetero)cycles of the formula (III)

-   -    in which    -   A, R⁶ and R⁷ have the meanings given above,    -   Y¹ represents O (oxygen),    -   X¹ represents O (oxygen) or NR⁸,    -   E represents chlorine, bromine, iodine, —OSO₂CF₃ or        —OSO₂(CF₂)₃CF₃,    -    in the presence of a catalyst, in the presence of a diboronic        ester and, where appropriate, in the presence of an acid binder        and, where appropriate, in the presence of a diluent,        or

-   B) reacting Δ¹-pyrrolines of the formula (IV)

-    in which    -   R¹, R², R⁴ and m have the meanings given above,    -   Z² represents —B(OH)₂,        (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,        (5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,        (4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or        1,3,2-benzodioxaborol-2-yl,    -   with (hetero)cycles of the formula (III)

-   -    in which    -   E, A, Y¹, X¹, R⁶ and R⁷ have the meanings given above,    -    in the presence of a catalyst, where appropriate in the        presence of an acid binder and, where appropriate, in the        presence of a diluent,        or

-   C) reacting Δ¹-pyrrolines of the formula (II)

-    in which    -   R¹, R², R⁴, m and Z¹ have the meanings given above with boronic        acid derivatives of the formula (V)

-   -    in which    -   Z², A, Y¹, X¹, R⁶ and R⁷ have the meanings given above in the        presence of a catalyst, where appropriate in the presence of an        acid binder and, where appropriate, in the presence of a        diluent,        or

-   D) reacting Δ¹-pyrrolines of the formula (II-a)

-   -    in which    -   R¹, R², R⁴ and m have the meanings given above,    -   Z³ represents bromine or iodine with organometallic compounds of        the formula (VI)

-   -    in which    -   A, Y¹, X¹, R⁶ and R⁷ have the meanings given above,    -   M represents ZnCl, Sn(Me)₃ or Sn(n-Bu)₃,    -    in the presence of a catalyst, where appropriate in the        presence of an acid binder and, where appropriate, in the        presence of a diluent,        or

-   E) reacting Δ¹-pyrrolines of the formula (VII)

-    in which    -   R¹, R², A, R⁴ and m have the meanings given above either with an        iso(thio)cyanate of the formula (VIII)        R⁷—N═C═Y  (VIII)    -    in which    -   Y and R⁷ have the meanings given above or with a (thio)carbonate        of the formula (IX)

-   -    in which    -   Y and R⁷ have the meanings given above,    -   X² represents O (oxygen) or S (sulphur),    -    in each case where appropriate in the presence of a diluent        and, where appropriate, in the presence of an acid binder.

Finally it has been found that the compounds of the formula (I)according to the invention possess very good insecticidal properties andmay be used both in crop protection and in the protection of materialsfor the purpose of controlling unwanted pests, such as insects.

The formula (I) provides a general definition of the Δ¹-pyrrolinesaccording to the invention.

Preferred compounds of the formula (I) are those in which

-   R¹ represents fluorine, chlorine, bromine or methyl,-   R² represents hydrogen, fluorine, chlorine or bromine,-   R³ represents —N(R⁶)—C(═Y)—X—R⁷,    and-   a) A represents arylene (especially phenylene) or 5-membered    heteroarylene having 1 to 3 heteroatoms, containing 0 to 3 nitrogen    atoms, 0 to 1 oxygen atom and/or 0 to 1 sulphur atom (in particular    from the series pyrrolylene, furylene, thienylene, pyrazylene,    imidazylene, triazylene, thiazylene or oxazylene), or 6-membered    heteroarylene having 3 nitrogen atoms (especially triazinylene) or    6-membered heteroarylene having 1 nitrogen atom and 1 to 2 further    heteroatoms, of which 0 to 2 may be oxygen atoms and/or 0 to 2 may    be sulphur atoms (in particular from the series oxazinylene or    thiazinylene), each being optionally substituted from one to three    times by identical or different substituents R⁵, and    -   Y represents O (oxygen) or S (sulphur) and    -   X represents O (oxygen), S (sulphur) or NR⁸,        or-   b) A represents pyridinylene, pyrimidinylene, pyrazinylene or    pyridazinylene each optionally substituted once or twice by    identical or different substituents R⁵, and    -   Y represents O (oxygen) or S (sulphur), and    -   X represents S (sulphur) or NR⁸,        or-   c) A represents pyridinylene, pyrimidinylene, pyrazinylene or    pyridazinylene each optionally substituted once or twice by    identical or different substituents R⁵, and    -   Y represents S (sulphur), and    -   X represents O (oxygen),        or-   d) A represents pyridinylene, pyrimidinylene, pyrazinylene or    pyridazinylene each optionally substituted once or twice by    identical or different substituents R⁵, and    -   Y represents O (oxygen), and    -   X represents O (oxygen),        and-   R⁴ and R⁵ independently of one another represents fluorine,    chlorine, bromine, C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₆-alkylthio,    C₁–C₆-haloalkyl, C₁–C₆-haloalkoxy or C₁–C₆-haloalkylthio,-   m represents 0, 1, 2 or 3,-   R⁶ represents hydrogen or C₁–C₆-alkyl,-   R⁷ and R⁸ independently of one another represent hydrogen or    represent C₁–C₂₀-alkyl or C₂–C₂₀-alkenyl each optionally substituted    one or more times by identical or different substituents selected    from the group consisting of fluorine, chlorine, bromine,    C₁–C₆-alkylcarbonyl, C₁–C₆-alkylcarbonyloxy, C₁–C₆-alkylamino,    di-(C₁–C₆-alkyl)amino, C₁–C₁₀-alkoxy, C₁–C₁₀-alkylthio,    C₁–C₁₀-alkoxy-C₁–C₁₀-alkoxy, C₁–C₁₀-haloalkoxy, C₁-₁₀-haloalkylthio    and C₁–C₁₀-haloalkoxy-C₁–C₁₀-alkoxy;    -   or represent C₃–C₁₂-cycloalkyl, C₃–C₇-cycloalkyl-C₁–C₄-alkyl,        aryl, aryl-C₁–C₄-alkyl, saturated or unsaturated 5- to        10-membered heterocyclyl or heterocyclyl-C₁–C₄-alkyl having 1 to        4 heteroatoms, containing 0 to 4 nitrogen atoms, 0 to 2        non-adjacent oxygen atoms and/or 0 to 2 non-adjacent sulphur        atoms (especially tetrazolyl, furyl, furfuryl, benzofuryl,        tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl,        pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl,        benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl,        benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl,        pyridazyl, pyrazinyl, piperidinyl, morpholinyl, thiomorpholinyl,        triazinyl, triazolyl, quinolinyl or isoquinolinyl) each        optionally substituted from one to four times by identical or        different substituents selected from the group consisting of        fluorine, chlorine, bromine, C₁–C₆-alkyl, C₁–C₆-alkoxy,        C₁–C₆-alkylthio, C₁–C₆-haloalkyl, C₁–C₆-haloalkoxy,        C₁–C₆-haloalkylthio, C₁–C₆-alkylcarbonyl and        C₁–C₆-alkoxycarbonyl,-   R⁶ and R⁷ further together represent C₂–C₄-alkylene optionally    substituted from one to four times by C₁–C₄-alkyl, or-   R⁷ and R⁸ further represent, together with the nitrogen atom to    which they are attached, a saturated or unsaturated 5- to    10-membered heterocycle which may optionally contain a further    heteroatom group from the series —O—, —S— or —NR⁹— and which may    optionally be substituted from one to four times by identical or    different substituents selected from the group consisting of    fluorine, chlorine, bromine, C₁–C₆-alkyl, C₁–C₆-alkoxy,    C₁–C₆-alkylthio, C₁–C₆-haloalkyl, C₁–C₆-haloalkoxy and/or    C₁–C₆-haloalkylthio, and-   R⁹ represents hydrogen, C₁–C₆-alkyl or C₂–C₆-alkenyl.-   Particularly preferred compounds of the formula (I) are those in    which-   R¹ represents fluorine, chlorine or methyl,-   R² represents hydrogen, fluorine or chlorine,-   R³ represents —N(R⁶)—C(═Y)—X—R⁷,    and-   a) A represents phenylene, pyrrolylene, furylene, thienylene,    pyrazylene, imidazylene, triazylene, thiazylene or oxazylene each    optionally substituted once or twice by identical or different    substituents R⁵, and    -   Y represents O (oxygen) or S (sulphur), and    -   X represents O (oxygen), S (sulphur) or NR⁸,        or-   b) A represents pyridinylene, pyrimidinylene, pyrazinylene or    pyridazinylene each optionally substituted once or twice by    identical or different substituents R⁵, and    -   Y represents O (oxygen) or S (sulphur), and    -   X represents S (sulphur) or NR⁸,        or-   c) A represents pyridinylene, pyrimidinylene, pyrazinylene or    pyridazinylene each optionally substituted once or twice by    identical or different substituents R⁵, and    -   Y represents S (sulphur), and    -   X represents O (oxygen),        or-   d) A represents pyridinylene, pyrimidinylene, pyrazinylene or    pyridazinylene each optionally substituted once or twice by    identical or different substituents R⁵, and    -   Y represents O (oxygen), and    -   X represents O (oxygen),        and-   R⁴ and R⁵ independently of one another represent fluorine, chlorine,    C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₄-alkylthio; C₁–C₄-haloalkyl,    C₁–C₄-haloalkoxy or C₁–C₄-haloalkylthio having in each case 1 to 9    fluorine, chlorine and/or bromine atoms,-   m represents 0, 1 or 2,-   R⁶ represents hydrogen or C₁–C₄-alkyl,-   R⁷ and R⁸ independently of one another represent hydrogen or    represent C₁–C₁₆-alkyl or C₂–C₁₆-alkenyl each optionally substituted    one or more times by identical or different substituents selected    from the group consisting of fluorine, chlorine, bromine,    C₁–C₄-alkylcarbonyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylamino,    di-(C₁–C₄-alkyl)amino, C₁–C₁₀-alkoxy, C₁–C₁₀-alkylthio,    C₁–C₁₀-alkoxy-C₁–C₆-alkoxy, C₁–C₁₀-haloalkoxy, C₁–C₁₀-haloalkylthio    and C₁–C₁₀-haloalkoxy-C₁–C₆-alkoxy having in each case 1 to 21    fluorine, chlorine and/or bromine atoms;    -   or represent C₃–C₁₀-cycloalkyl, C₃–C₆-cycloalkyl-C₁–C₄-alkyl,        phenyl, benzyl, phenylethyl, tetrazolyl, furyl, furfuryl,        benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl,        thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl,        oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl,        thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl,        pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl, morpholinyl,        thiomorpholinyl, triazinyl, triazolyl, quinolinyl or        isoquinolinyl each optionally substituted from one to three        times by identical or different substituents selected from the        group consisting of fluorine, chlorine, bromine, C₁–C₄-alkyl,        C₁–C₄-alkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkyl,        C₁–C₄-haloalkoxy, C₁–C₄-haloalkylthio having in each case 1 to 9        fluorine, chlorine and/or bromine atoms, C₁–C₄-alkylcarbonyl and        C₁–C₄-alkoxycarbonyl,-   R⁶ and R⁷ further together represent C₂–C₃-alkylene optionally    substituted from one to three times by C₁–C₄-alkyl, or-   R⁷ and R⁸ further represent, together with the nitrogen atom to    which they are attached, a saturated or unsaturated 5- to 7-membered    heterocycle which may optionally contain a further heteroatom group    from the series —O—, —S— or —NR⁹— (in particular from the series    piperidino, morpholino, thiomorpholino, piperazino, pyrrolidino,    oxazolidino, thiazolidino, 4H-1-oxazinyl, 4H-1-thiazinyl) and which    may optionally be substituted from one to four times by identical or    different substituents selected from the group consisting of    fluorine, chlorine, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₄-alkylthio,    C₁–C₄-haloalkyl, C₁–C₄-haloalkoxy and/or C₁–C₄-haloalkylthio having    in each case 1 to 9 fluorine, chlorine and/or bromine atoms, and-   R⁹ represents hydrogen, C₁–C₄-alkyl or C₂–C₄-alkenyl.-   Very particularly preferred compounds of the formula (I) are those    in which-   R¹ represents fluorine or chlorine,-   R² represents hydrogen or fluorine,-   R³ represents —N(R⁶)—C(═Y)—X—R⁷,    and-   a) A represents 1,2-phenylene, 1,4-phenylene, 2,5-pyrrolylene,    2,5-furylene, 2,4-furylene, 2,5-thienylene, 2,4-thienylene,    2,5-thiazylene, 2,4-thiazylene, 2,5-oxazylene or 2,4-oxazylene each    optionally substituted once by R⁵, and    -   Y represents O (oxygen) or S (sulphur), and    -   X represents O (oxygen), S (sulphur) or NR⁸,        or-   b) A represents 2,5-pyridinylene, 2,5-pyrimidinylene,    2,5-pyrazinylene or 3,6-pyridazinylene each optionally substituted    once by R⁵, and    -   Y represents O (oxygen) or S (sulphur), and    -   X represents S (sulphur) or NR⁸,        or-   c) A represents 2,5-pyridinylene, 2,5-pyrimidinylene,    2,5-pyrazinylene or 3,6-pyridazinylene each optionally substituted    once by R⁵, and    -   Y represents S (sulphur), and    -   X represents O (oxygen),        or-   d) A represents 2,5-pyridinylene, 2,5-pyrimidinylene,    2,5-pyrazinylene or 3,6-pyridazinylene each optionally substituted    once by R⁵, and    -   Y represents O (oxygen), and    -   X represents O (oxygen),        and-   R⁴ and R⁵ independently of one another represent fluorine, chlorine,    methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl,    t-butyl, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,    s-butoxy, t-butoxy, methylthio, ethylthio, n-propylthio,    i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio,    trifluoromethyl, trifluoroethyl, trifluoromethoxy, trifluoroethoxy,    trifluoromethylthio or trifluoroethylthio,-   m represents 0 or 1,-   R⁶ represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl,    i-butyl, s-butyl or t-butyl,-   R⁷ and R⁸ independently of one another represent hydrogen or    represent C₁–C₁₀-alkyl or C₂–C₁₀-alkenyl (especially methyl, ethyl,    n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, the isomeric    pentyls, the isomeric hexyls) each optionally substituted one or    more times by identical or different substituents selected from the    group consisting of fluorine, chlorine, bromine,    C₁–C₄-alkylcarbonyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylamino,    di-(C₁–C₄-alkyl)amino, C₁–₁₀-alkoxy, C₁–C₈-alkoxy-C₁–C₆-alkoxy,    C₁–C₁₀-alkylthio, C₁–C₁₀-haloalkoxy, C₁–C₁₀-haloalkylthio having in    each case 1 to 21 fluorine, chlorine and/or bromine atoms,    C₁–C₈-haloalkoxy-C₁–C₆-alkoxy having 1 to 17 fluorine, chlorine    and/or bromine atoms;    -   or represent C₃–C₈-cycloalkyl, cyclopropylmethyl,        cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl,        cyclopentylethyl, cyclohexylethyl, phenyl, benzyl, phenylethyl,        tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl,        thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl,        pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl,        imidazolyl, pyrazolyl, thiazolyl, benzothiazolyl, thiazolidinyl,        pyridinyl, pyrimidinyl, pyridazyl, pyrazinyl, piperidinyl,        morpholinyl, thiomorpholinyl, triazinyl, triazolyl, quinolinyl        or isoquinolinyl each optionally substituted from one to three        times by identical or different substituents selected from the        group consisting of fluorine, chlorine, bromine, C₁–C₄-alkyl,        C₁–C₄-alkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkyl,        C₁–C₄-haloalkoxy, C₁–C₄-haloalkylthio having in each case 1 to 9        fluorine, chlorine and/or bromine atoms, C₁–C₄-alkylcarbonyl and        C₁–C₄-alkoxycarbonyl,-   R⁶ and R⁷ together further represent methylene or ethylene each    optionally substituted once or twice by identical or different    methyl, ethyl, n-propyl or i-propyl substituents, or-   R⁷ and R⁸ further represent, together with the nitrogen atom to    which they are attached, a 5- to 6-membered heterocycle from the    series piperidino, morpholino, thiomorpholino, piperazino,    pyrrolidino, oxazolidino, thiazolidino, 4H-1-oxazinyl,    4H-1-thiazinyl which may optionally be substituted from one to four    times by identical or different substituents selected from the group    consisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl,    i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, methoxy, ethoxy,    n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy,    methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio,    i-butylthio, s-butylthio, t-butylthio, C₁–C₄-haloalkyl,    C₁–C₄-haloalkoxy, C₁–C₄-haloalkylthio having in each case 1 to 9    fluorine, chlorine and/or bromine atoms, the piperazino radical    being substituted on the second nitrogen atom by R⁹, and-   R⁹ represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl,    i-butyl, s-butyl, t-butyl, vinyl or allyl.

Further very particularly preferred compounds are those of the formulae(I-1) and (I-2)

in each of which

-   a) Y represents O (oxygen) or S (sulphur), and    -   X represents O (oxygen), S (sulphur) or NR⁸,        and R¹, R², R⁴, R⁵, m, R⁶, R⁷, R⁸ have the meanings given above.

In the formulae (I-1) and (I-2) the radicals R¹, R², R⁴, R⁵, m, R⁶, R⁷,R⁸ each represent with preference, with particular preference or withvery particular preference those definitions stated as being preferred,particularly preferred, etc. for these radicals in the context of thedescription of the substances of the formula (I) according to theinvention. Y and X represent in each case with preference, withparticular preference or with very particular preference thosedefinitions described in each case under the corresponding section “a)”.

Further very particularly preferred compounds are those of the formulae(I-3) to (I-8)

in each of which

-   p represents 0, 1 or 2,-   b) Y represents O (oxygen) or S (sulphur), and    -   X represents S (sulphur) or NR⁸,        or-   c) Y represents S (sulphur), and    -   X represents O (oxygen),        or-   d) Y represents O (oxygen), and    -   X represents O (oxygen),-   and R¹, R², R⁴, R⁵, m, R⁶, R⁷ and R⁸ have the meanings given above.

In the formulae (I-3) to (I-8) the radicals R¹, R², R⁴, R⁵, m, R⁶, R⁷,R⁸ each represent with preference, with particular preference or withvery particular preference those definitions stated as being preferred,particularly preferred, etc. for these radicals in the context of thedescription of the substances of the formula (I) according to theinvention. Y and X represent in each case with preference, withparticular preference or with very particular preference thosedefinitions described in each case under the corresponding section “a)”,“b)”, “c)” and “d)”. p represents preferably 0, 1 or 2, with particularpreference 0 or 1, with very particular preference 0.

Further preferred compounds of the formula (I) are those in which Arepresents phenylene, preferably 1,4-phenylene.

Further preferred compounds of the formula (I) are those in which Arepresents pyridinylene, pyrimidinylene, pyrazinylene or pyridazinylene,preferably 2,5-pyridinylene, 2,5-pyrimidinylene, 2,5-pyrazinylene or3,6-pyridazinylene.

Further preferred compounds of the formula (I) are those in which Yrepresents O (oxygen).

Further preferred compounds of the formula (I) are those in which Xrepresents O (oxygen) or NR⁸, preferably O (oxygen).

Further preferred compounds of the formula (I) are those in which Y andX each represent O (oxygen).

Further preferred compounds of the formula (I) are those in which Yrepresents O (oxygen) and X represents NR⁸.

Further preferred compounds of the formula (I) are those in which Arepresents phenylene, preferably 1,4-phenylene, Y represents O (oxygen)or S (sulphur), preferably O (oxygen), and X represents O (oxygen), S(sulphur) or NR⁸, preferably O (oxygen) or NR⁸, with particularpreference O (oxygen).

Further preferred compounds of the formula (I) are those in which R¹ andR² each represents fluorine.

Further preferred compounds of the formula (I) are those in which R¹represents methyl and R² represents hydrogen.

Further preferred compounds of the formula (I) are those in which R¹represents chlorine and R² represents hydrogen.

Further preferred compounds of the formula (I) are those in which R¹represents chlorine and R² represents fluorine.

Further preferred compounds of the formula (I) are those in which R⁶represents hydrogen.

Further preferred compounds of the formula (I-a) are those with (R)configuration in position 5 of the pyrroline ring.

in which

-   R¹, R², A, R³, R⁴ and m have the meanings given above.

In accordance with formula (I-a), the compounds (I-1) to (I-8) may alsobe present with R configuration in position 2 of the 2H-pyrrole(corresponding to position 5 when named as pyrroline).

Compounds of the formula (I-a) are obtained by customary methods ofoptical resolution, such as, for example, by chromatographing thecorresponding racemates on a chiral stationary phase. It is possible toseparate either the racemic end products or racemic intermediates inthis way into the two enantiomers.

Saturated hydrocarbon radicals such as alkyl, alone or in conjunctionwith heteroatoms, such as in alkoxy, for example, may where possible ineach case be straight-chain or branched.

The radical definitions and elucidations set out above in general or inranges of preference may, however, also be combined as desired with oneanother, i.e. are arbitrary combinations between the respective rangesand ranges of preference. They apply both to the end products and to theprecursors and intermediates accordingly.

Using 5-(2,6-difluorophenyl)-2-(4-bromophenyl)-3,4-dihydro-2H-pyrrole,methyl 4-bromophenylcarbamate and4,4,4′,4′,5,5,′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane as startingmaterials and a palladium catalyst, the course of the process (A)according to the invention can be illustrated by the following equation.

Using5-(2,6-difluorophenyl)-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl]-3,4-dihydro-2H-pyrroleand methyl 4-bromophenylcarbamate as starting materials and a palladiumcatalyst, the course of the process (B) according to the invention canbe illustrated by the following equation.

Using5-(2,6-difluorophenyl)-2-[4-(trifluoromethylsulfonyloxy)phenyl]-3,4-dihydro-2H-pyrroleand methyl4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenylcarbamate asstarting materials and a palladium catalyst, the course of the process(C) according to the invention can be illustrated by the followingequation.

Using 5-(2,6-difluorophenyl)-2-(4-bromophenyl)-3,4-dihydro-2H-pyrroleand methyl 4-(tributylstannyl)phenylcarbamate as starting materials anda palladium catalyst, the course of the process (D) according to theinvention can be illustrated by the following equation.

Using4′-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]-1,1′-biphenyl-4-amineand (methylimino)(thioxo)methane as starting material, the course of theprocess (E) according to the invention can be illustrated by thefollowing equation.

Elucidation of the Processes and IntermediatesProcess (A)

In a first reaction step, a compound of the formula (II) is coupled witha diboronic acid ester in the presence of a palladium catalyst, ifappropriate in the presence of an acid binder and if appropriate in thepresence of a solvent. Without any isolation of the intermediate, acompound of the formula (III) is coupled in the same reaction vessel ina second reaction step in the presence of a catalyst, if appropriate inthe presence of an acid binder and if appropriate in the presence of asolvent (cf., for example, Tetrahedron Lett. 1997, 38, 3841).

The process (A) according to the invention can be carried out in twovariants. It is possible either to initially charge a compound of theformula (II) or to initially charge a compound of the formula (III).Process (A) is to be considered a tandem reaction of the processes (B)and (C) described below.

The formula (II) provides a general definition of the Δ¹-pyrrolinesrequired as starting materials for carrying out the process (A). In thisformula, R¹, R², R³ and m preferably, particularly preferably and veryparticularly preferably have those meanings which have already beenmentioned in connection with the description of the substances of theformula (I) according to the invention as being preferred, particularlypreferred, etc. for these radicals. Z preferably represents bromine,iodine, —OSO₂CF₃ or —OSO₂(CF₂)₃CF₃, particularly preferably bromine,—OSO₂CF₃ or —OSO₂(CF₂)₃CF₃, very particularly preferably bromine or—OSO₂CF₃.

Δ¹-Pyrrolines of the formula (II) can be prepared by known processes(cf. WO 98/22438). Δ¹-Pyrrolines of the formula (II) can also beobtained by a process which is described below.

The formula (III) provides a general definition of the (hetero)cyclesrequired as starting materials for carrying out the process (A)according to the invention. In this formula, Y¹ preferably represents O(oxygen). X¹ preferably represents O (oxygen) or NR⁸. E preferablyrepresents bromine, chlorine, iodine or —OSO₂CF₃, with particularpreference bromine, chlorine or iodine, with very particular preferencebromine or chlorine. A, R⁶, R⁷ and R⁸ represent preferably, withparticular preference or with very particular preference thosedefinitions already stated as being preferred, particularly preferred,etc. for these radicals in connection with the description of thesubstances of the formula (I) according to the invention.

The (hetero)cycles of the formula (III) are known in some cases.

(Hetero)cycles of the Formula (III-a)

in which

-   E, A, Y¹, X¹ and R⁷ have the meanings given above,-   R^(6-a) represents hydrogen,    may be prepared, for example, by-   a) reacting isocyanates of the formula (X)    E-A-N═C═O  (X)-    in which    -   E and A have the meanings given above,    -   with alcohols and/or amines of the formula (XI)        H—X¹—R⁷  (XI)-    in which    -   X¹ and R⁷ have the meanings given above,    -   or with compounds of the formula (XII)

-   -    in which    -   X has the meanings given above,    -   L represents alkylene optionally substituted one or more times        by alkyl    -   optionally in the presence of a diluent (e.g. toluene, dioxane,        dimethyl sulphoxide).

The formula (III-a) provides a general definition of the (hetero)cycleswhich can be prepared by process (a). In this formula, A and R⁷preferably, with particular preference or with very particularpreference represent those definitions already stated as beingpreferred, particularly preferred, etc. for these radicals in connectionwith the description of the substances of the formula (I) according tothe invention. E, Y¹ and X¹ represent preferably, with particularpreference or with very particular preference those definitions alreadystated as being preferred, particularly preferred, etc. for theseradicals in connection with the description of the substances of theformula (III) according to the invention. R^(6-a) preferably representshydrogen.

The formula (X) provides a general definition of the isocyanatesrequired as starting materials for carrying out the process (a). In thisformula, A represents preferably, with particular preference or withvery particular preference those definitions already stated as beingpreferred, particularly preferred, etc., for these radicals inconnection with the description of the substances of the formula (I)according to the invention. E represents preferably, with particularpreference or with very particular preference those definitions alreadystated as being preferred, particularly preferred, etc. for theseradicals in connection with the description of the substances of theformula (III) according to the invention.

Isocyanates of the formula (X) are known.

The formula (XI) provides a general definition of the alcohols and/oramines required as starting materials for carrying out the process (a).In this formula, R⁷ represents preferably, with particular preference orwith very particular preference those definitions already stated asbeing preferred, particularly preferred, etc. for these radicals inconnection with the description of the substances of the formula (I)according to the invention. X¹ represents preferably, with particularpreference or with very particular preference those definitions alreadystated as being preferred, particularly preferred, etc. for theseradicals in connection with the description of the substances of theformula (III) according to the invention.

Alcohols and amines of the formula (XI) are known.

The formula (XII) provides a general definition of the compoundsadditionally required as starting materials for carrying out the process(a). In this formula, X¹ represents preferably, with particularpreference or with very particular preference those definitions alreadystated as being preferred, particularly preferred, etc. for theseradicals in connection with the description of the substances of theformula (III) according to the invention. L represents preferablyC₂–C₄-alkylene optionally substituted from one to four times byC₁–C₄-alkyl, particularly preferably C₂–C₃-alkylene optionallysubstituted from one to three times by C₁–C₄-alkyl, with very particularpreference methylene or ethylene each optionally substituted once ortwice by identical or different methyl, ethyl, n-propyl or i-propylsubstituents. Compounds of the formula (XII) are known.

(Hetero)cycles of the Formula (III-b)

in which

-   E, A, Y¹ and R⁷ have the meanings given above,-   X³ represents O (oxygen),-   R^(6-b) represents alkyl,    may be prepared, for example, by-   b) reacting amines of the formula (XIII)

-    in which    -   E, A and R^(6-b) have the meanings given above,    -   with a chloroformate of the formula (XIV)

-   -    in which    -   R⁷ has the meanings given above,    -   in the presence of N,O-bis(trimethylsilyl)acetamide and, where        appropriate, in the presence of a diluent (e.g. dichloromethane)        (cf. Syn. Commun. 1985, 15, 1025–1031).

The formula (III-b) provides a general definition of the (hetero)cycleswhich can be prepared by the process (b). In this formula, A representspreferably, with particular preference or with very particularpreference those definitions already stated as being preferred,particularly preferred, etc. for these radicals in connection with thedescription of the substances of formula (I) according to the invention.E represents preferably, with particular preference or with veryparticular preference those definitions already stated as beingpreferred, particularly preferred, etc. for these radicals in connectionwith the description of the substances of formula (III) according to theinvention. R^(6-b) represents preferably C₁–C₆-alkyl, with particularpreference C₁–C₄-alkyl, with very particular preference methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl.

The formula (XIII) provides a general definition of the amines requiredas starting materials for carrying out the process (d). In this formula,E and A represent preferably, with particular preference or with veryparticular preference those definitions already stated as beingpreferred, particularly preferred, etc. for these radicals in connectionwith the description of the substances of formula (I) according to theinvention. R^(6-b) represents preferably C₁–C₆-alkyl, with particularpreference C₁–C₄-alkyl, with very particular preference methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl.

Amines of the formula (XIII) are known.

The formula (XIV) provides a general definition of the chloroformatesrequired as starting materials for carrying out the process (b). In thisformula, R⁷ represents preferably, with particular preference or withvery particular preference those definitions already stated as beingpreferred, particularly preferred, etc. for these radicals in connectionwith the description of the substances of formula (I) according to theinvention.

Chloroformates of the formula (XIV) are known.

(Hetero)cycles of the formula (III-c)

in which

-   E, A and Y¹ have the meanings given above,-   X³ represents O (oxygen),-   R^(6-c) and R^(7-c) together represent alkylene optionally    substituted one or more times by alkyl,    may be prepared, for example, by-   c) reacting isocyanates of the formula (X)    E-A-N═C═O  (X)    -    in which    -   E and A have the meanings given above,    -   with a dioxolane of the formula (XV)

-   -    in which    -   R^(6-c) and R^(7-c) have the meanings given above, where        appropriate in the presence of an acid binder (e.g. caesium        fluoride) and, where appropriate, in the presence of a diluent        (e.g. dimethyl sulphoxide) (cf. JP 2000-290265).

The formula (III-c) provides a general definition of the (hetero)cycleswhich can be prepared by process (c). In this formula, A representspreferably, with particular preference or with very particularpreference those definitions already stated as being preferred,particularly preferred, etc. for these radicals in connection with thedescription of the substances of formula (I) according to the invention.E represents preferably, with particular preference or with veryparticular preference those definitions already stated as beingpreferred, particularly preferred, etc. for these radicals in connectionwith the description of the substances of formula (III) according to theinvention. R^(6-c) and R^(7-c) together represent preferablyC₂–C₄-alkylene optionally substituted from one to four times byC₁–C₄-alkyl, with particular preference C₂–C₃-alkylene optionallysubstituted from one to three times by C₁–C₄-alkyl, with very particularpreference methylene or ethylene substituted once or twice by methyl,ethyl, n-propyl or i-propyl.

The isocyanates of the formula (X) required as starting materials forcarrying out the process (c) have already been described in connectionwith the elucidation of the process (a).

The formula (XV) provides a general definition of the dioxolanesrequired as starting materials for carrying out the process (c). In thisformula, R^(6-c) and R^(7-c) preferably, with particular preference andwith very particular preference represent those definitions alreadystated as being preferred, particularly preferred, for these radicals inconnection with the description of the substances of formula (III-c).

Dioxolanes of the formula (XV) are known.

Suitable diboronic esters for carrying out process (A) according to theinvention are 4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane,5,5,540 ,5′-tetramethyl-2,2′-bis-1,3,2-dioxaborinane,4,4,4′,4′,6,6′-hexamethyl-2,2′-bis-1,3,2-dioxaborinane or2,2′-bis-1,3,2-benzodioxaborole. Preference is given to using4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane,5,5,5′,5′-tetramethyl-2,2′-bis-1,3,2-dioxaborinane or4,4,4′,4′,6,6′-hexamethyl-2,2′-bis-1,3,2-dioxaborinane, particularlypreferably 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolaneor 5,5,5′,5′-tetramethyl-2,2′-bis-1,3,2-dioxaborinane, very particularlypreferably 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane.

When carrying out the process (A) according to the invention, in general1 mol or a slight excess of a diboronic ester and 1 mol or a slightexcess of a compound of the formula (III), and 3% of a palladiumcatalyst, are employed per mole of the compound of the formula (II).However, it is also possible to employ the reaction components in otherratios. It is possible to initially charge the compound of the formula(II) or, alternatively, the compound of the formula (III). Work-up iscarried out by customary methods. In general, the reaction mixture isdiluted with water and extracted with ethyl acetate. The organic phaseis washed, dried, filtered and concentrated. The residue is, ifappropriate, freed from any impurities that may still be present usingcustomary methods, such as chromatography or recrystallization.

Process (B)

The formula (IV) provides a general definition of the Δ¹-pyrrolinesrequired as starting materials for carrying out the process (B)according to the invention. In this formula, R¹, R², R⁴ and mpreferably, particularly preferably and very particularly preferablyhave those meanings which have already been mentioned in connection withthe description of the substances of the formula (I) according to theinvention as being preferred, particularly preferred, etc. for theseradicals. Z² preferably represents(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or 1,3,2-benzodioxaborol-2-yl,particularly preferably (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl or(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl, very particularly preferably(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl or(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl.

Δ¹-Pyrrolines of the formula (IV) can be prepared by

-   d) reacting compounds of the formula (II)

-    in which    -   R¹, R², R⁴, m and Z¹ have the meanings given above, with a        diboronic ester in the presence of a catalyst, if appropriate in        the presence of an acid binder and if appropriate in the        presence of a diluent (cf. J. Org. Chem. 1995, 60, 7508;        Tetrahedron Lett. 1997, 38, 3447).

Diboronic esters suitable for carrying out the process (d) have alreadybeen mentioned in the description of the process (A) according to theinvention.

The heterocycles of the formula (III) required as starting materials forcarrying out the process (B) according to the invention have alreadybeen described above in the description of process (A).

When carrying out the process (B) according to the invention, in general1 mol or a slight excess of a compound of the formula (III) is employedper mole of the compound of the formula (V). However, it is alsopossible to employ the reaction components in other ratios. Work-up iscarried out by customary methods. In general, the reaction mixture istaken up in ethyl acetate and the organic phase is washed with water,dried over sodium sulphate, filtered and concentrated. The residue is,if appropriate, freed from any impurities that may still be presentusing customary methods, such as chromatography or recrystallization.

Process (C)

The Δ¹-pyrrolines of the formula (II) required as starting materials forcarrying out the process (C) according to the invention have alreadybeen described in the description of process (A).

The formula (V) provides a general definition of the boronic acidderivatives required as starting materials for carrying out the process(C) according to the invention. In this formula, Y¹ representspreferably O (oxygen). X¹ represents preferably O (oxygen) or NR⁸. Z²represents preferably (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or 1,3,2-benzodioxaborol-2-yl,particularly preferably (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl or(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl, very particularly preferably(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl or(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl. A, R⁶, R⁷ and R⁸ representpreferably, with particular preference or with very particularpreference those definitions already stated as being preferred,particularly preferred, etc. for these radicals in connection with thedescription of the substances of the formula (I) according to theinvention.

The compounds of the formula (V) are known or can be prepared by knownprocesses.

When carrying out the process (C) according to the invention, in general1 mol or a slight excess of a compound of the formula (V) is employedper mole of the compound of the formula (II). However, it is alsopossible to employ the reaction components in other ratios. Work-up iscarried out by customary methods. In general, the reaction mixture istaken up in ethyl acetate and the organic phase is washed with water,dried over sodium sulphate, filtered and concentrated. The residue is,if appropriate, freed from any impurities that may still be presentusing customary methods, such as chromatography or recrystallization.

Process (D)

The formula (II-a) provides a general definition of the Δ¹-pyrrolinesrequired as starting materials for carrying out the process (D)according to the invention. In this formula, R¹, R², R⁴ and mpreferably, particularly preferably and very particularly preferablyhave those meanings which have already been mentioned in connection withthe description of the substances of the formula (I) according to theinvention as being preferred, particularly preferred, etc., for theseradicals. Z³ preferably represents bromine or iodine.

Δ¹-Pyrrolines of the formula (II-a) can be prepared by known processes(cf. WO 98/22438).

The formula (VI) provides a general definition of the organometalliccompounds required as starting materials for carrying out the process(D) according to the invention. In this formula, Y¹ representspreferably O (oxygen). X¹ represents preferably O (oxygen) or NR⁸. Mrepresents preferably ZnCl, Sn(Me)₃ or Sn(n-Bu)₃. A, R⁶, R⁷ and R⁸represents preferably, with particular preference or with veryparticular preference those definitions already stated as beingpreferred, particularly preferred, etc. for these radicals in connectionwith the description of the substances of formula (I) according to theinvention.

Organometallic compounds of the formula (VI) are known in some cases orcan be prepared by known methods. It is possible, for example, toprepare compounds of the formula (VI) in situ from the correspondingcompounds of the formula (III) in which X represents —OSO₂CF₃ (cf.Tetrahedron Lett. 1995, 36, 9085).

When carrying out the process (D) according to the invention, in general1 mol or a slight excess of a compound of the formula (VI) is employedper mole of the compound of the formula (II-a). However, it is alsopossible to employ the reaction components in other ratios. Work-up iscarried out by customary methods. In general, the reaction mixture istaken up in ethyl acetate and the organic phase is washed with water,dried over sodium sulphate, filtered and concentrated. The residue is,if appropriate, freed from any impurities that may still be presentusing customary methods, such as chromatography or recrystallization.

Preparation of Starting Materials for Processes (A), (B), (C) and (D)

The Δ¹-pyrrolines of the formulae (II), (IV) and (II-a) required asstarting materials for carrying out the processes (A), (B), (C) and (D)according to the invention may also be prepared by

-   e) reacting amides of the formula (XVI)

-    in which    -   Q represents Z¹, Z² or Z³,    -   R¹⁰ represents alkyl, haloalkyl, phenyl or benzyl,    -   R¹, R², R⁴, m, Z¹, Z² and Z³ have the meanings given above, with        an N-deacylating agent in the presence of a diluent.

The formula (XVI) provides a general definition of the amides requiredas starting materials for carrying out the process (e). In this formula,R¹, R², R⁴ and m represent preferably, with particular preference orwith very particular preference those definitions already stated asbeing preferred, particularly preferred, etc. for these radicals inconnection with the description of the substances of the formula (I)according to the invention. Q represents Z¹, Z² or Z³ or represents thepreferred, particularly preferred and very particularly preferreddefinitions of these radicals which have already been described above.R¹⁰ represents preferably C₁–C₄-alkyl, C₁–C₄-haloalkyl, phenyl orbenzyl, with particular preference methyl, ethyl, phenyl or benzyl, withvery particular preference methyl, phenyl or benzyl.

The amides of the formula (XVI) required as starting materials forcarrying out the process (e) may be prepared by

-   f) reacting cyclopropanes of the formula (XVII)

-    in which R¹, R², R⁴, m and Q have the meanings given above,    -   with nitrites of the formula (XVIII)        R¹⁰—CN  (XVIII)    -    in which R¹⁰ has the meanings given above    -   and a protic acid or trimethylsilyl tetrafluoroborate.

The formula (XVII) provides a general definition of the cyclopropanesrequired as starting materials for carrying out the process (f). In thisformula, R¹, R², R⁴ and m represent preferably, with particularpreference or with very particular preference those definitions alreadystated as being preferred, particularly preferred or very particularlypreferred for these radicals in connection with the description of thesubstances of the formula (I) according to the invention. Q representsZ¹, Z² or Z³ or represents the preferred, particularly preferred andvery particularly preferred definitions of these radicals which havealready been described above.

The formula (XVIII) provides a general definition of the nitrilesrequired as starting materials for carrying out the process (f). In thisformula, R¹⁰ represents preferably C₁–C₄-alkyl, C₁–C₄-haloalkyl, phenylor benzyl, with particular preference methyl, ethyl, phenyl or benzyl,with very particular preference methyl, phenyl or benzyl.

Suitable protic acids when carrying out process (f) include all acidswhich can commonly be used for this purpose. A preferred possibility foruse is sulphuric acid.

As trimethylsilyltetrafluoroborate for carrying out process (f), thecompound of the formula (XIX)Me₃Si—N═C⁺—CH₃BF₄ ⁻  (XIX)is suitable. The reagent of the formula (XIX) is known (cf. TetrahedronLett. 1984, 25, 577–578).

The reaction temperatures for carrying out process (f) may be variedwithin a relatively wide range. It is normal to operate at temperaturesbetween −20° C. and +60° C., preferably between −10° C. and 30° C.

The cyclopropanes of the formula (XVII) required as starting materialsfor carrying out the process (f) may be prepared by

-   g) reacting chalcones of the formula (XX)

-    in which    -   R¹, R², R⁴, m and Q have the meanings given above, with a        trialkylsulphoxonium ylide in the presence of a base and, where        appropriate, in the presence of a diluent.

The formula (XX) provides a general definition of the chalcones requiredas starting materials when carrying out the process (g). In thisformula, R¹, R², R⁴ and m represent preferably, with particularpreference or with very particular preference those definitions alreadystated as being preferred, particularly preferred or very particularlypreferred for these radicals in connection with the description of thesubstances of the formula (I) according to the invention. Q representsZ¹, Z² or Z³ or represents a preferred, particularly preferred and veryparticularly preferred definition of these radicals which have alreadybeen described above.

As a trialkylsulphoxonium ylide for carrying out the process (g) it ispreferred to use trimethylsulphoxonium ylide.

As bases when carrying out process (g) it is possible to use alkalimetal hydrides, alkoxides and hydroxides. Preference is given to usingsodium hydride, potassium 2-methyl-2-propoxide, sodium methoxide orpotassium hydroxide, with particular preference sodium hydride.

Suitable diluents when carrying out process (g) include dimethylsulphoxide, tetrahydrofuran, acetonitrile, toluene or diethylene glycol,and mixtures thereof. It is preferred to use dimethyl sulphoxide (cf.Tetrahedron Asymmetry 1998, 9, 1035).

The reaction temperatures for carrying out process (g) according to theinvention may be varied within a relatively wide range. It is normal tooperate at temperatures between −20° C. and +120° C., preferably between0° C. and 60° C., with particular preference between 20° C. and 40° C.

The chalcones of the formula (XX) required as starting materials forcarrying out process (g) are known.

When carrying out process (e), the amides of the formula (XVI) areN-deacylated in the reaction to give pyrrolines of the formulae (II),(IV), and (II-a) using protic acids (cf. J. Org. Chem. 1978, 43, 4593),inorganic bases (cf. J. Chem. Soc. 1964, 4142), hydrazines (cf. J. Org.Chem. 1978, 43, 3711) or biotransformation with enzymes (cf. Appl.Microbiol. Biotechnol. 1997, 47, 650). Other customary methods ofdeacylating amides are described in T. W. Greene, P. G. M. Wuts,Protective Groups in Organic Synthesis (Ed. 3, New York, Wiley 1999, pp.553–555).

As N-deacylating agents it is preferred to use protic acids or organicacids, with particular preference aqueous hydrochloric acid, aqueoushydrobromic acid or trifluoroacetic acid, with very particularpreference aqueous hydrochloric acid; preferably inorganic bases, withparticular preference barium hydroxide [Ba(OH)₂] and sodium hydroxide(NaOH) and preferably biotransformations, with particular preferenceusing acylases.

In the case of N-deacylation by means of biotransformations, thecompounds of the formulae (II), (IV), and (II-a) are obtained with oneof the two enantiomers in excess.

Suitable diluents when carrying out process (e) include water oralcohols and mixtures of these. Preference is given to using water,methanol or ethanol or mixtures of two or three of these three diluents.

The reaction temperatures when carrying out process (e) may be variedwithin a relatively wide range. It is normal to operate at temperaturesbetween 20° C. and 200° C., preferably between 60° C. and 140° C., withparticular preference between 80° C. and 120° C. Where the N-deacylationis carried out enzymatically using acylases, it is normal to operatebetween 20° C. and 60° C., preferably between 20° C. and 40° C.

When carrying out process (e) it is normal to use 2 parts by volume of aprotic acid per part by volume of a 10% strength (w/v) alcoholicsolution of amide of the formula (XVI). However, other ratios of thereaction components may also be chosen. Work-up is carried out bycustomary methods. In general, the reaction mixture is neutralized withsodium hydroxide solution and then extracted with ethyl acetate and theorganic phase is dried, filtered and concentrated.

Process (E)

The formula (VII) provides a general definition of the Δ¹-pyrrolinesrequired as starting materials when carrying out the process (E)according to the invention. In this formula, R¹, R², A, R⁴ and mrepresent preferably, with particular preference or with very particularpreference those definitions already stated as being preferred,particularly preferred, etc. for these radicals in connection with thedescription of the substances of formula (I) according to the invention.

Δ¹-Pyrrolines of the formula (VII) are novel. They may be prepared by

-   h) reacting Δ¹-pyrrolines of the formula (I-b)

-    in which    -   R¹, R², A, R⁴, m and R⁷ have the meanings given above, with a        mineral acid (e.g. hydrochloric acid, sulphuric acid) or a base        (e.g. sodium hydroxide, potassium hydroxide) where appropriate        in the presence of a diluent (e.g. alcohols such as methanol,        ethanol or water or mixtures of these).

The Δ¹-pyrrolines of the formula (I-b) required as starting materialswhen carrying out the process (h) are a subgroup of the compounds of theformula (I) according to the invention. In the formula (I-b), R¹, R², A,R⁴, m and R⁷ represent preferably, with particular preference or withvery particular preference those definitions already stated as beingpreferred, particularly preferred, etc. for these radicals in connectionwith the description of the substances of the formula (I) according tothe invention. Δ¹-Pyrrolines of the formula (I-b) may be prepared by oneof the processes (A), (B), (C) or (D) according to the invention.

The formula (VIII) provides a general definition of theiso(thio)cyanates required as starting materials when carrying out theprocess (E) of the invention. In this formula, Y and R⁷ representpreferably, with particular preference or with very particularpreference those definitions already stated as being preferred,particularly preferred, etc. for these radicals in connection with thedescription of the substances of the formula (I) according to theinvention.

Iso(thio)cyanates of the formula (VIII) are known and/or may be preparedby known processes.

The formula (IX) provides a general definition of the (thio)carbonatesrequired as starting materials when carrying out the process (E) of theinvention. In this formula, Y and R⁷ represent preferably, withparticular preference or with very particular preference thosedefinitions already stated as being preferred, particularly preferred,etc. for these radicals in connection with the description of thesubstances of the formula (I) according to the invention. X² representspreferably O (oxygen) or S (sulphur).

(Thio)carbonates of the formula (IX) are known and/or may be prepared byknown processes.

When carrying out the process (E) according to the invention, in general1 mol or a slight excess of a compound of the formula (VIII) and/or 1mol or a slight excess of a compound of the formula (IX) are employedper mole of compound of the formula (VII). However, it is also possibleto employ the reaction components in other proportions. Work-up iscarried out by customary methods. In general, the reaction mixture istaken up in ethyl acetate and the organic phase is washed with water,dried over sodium sulphate, filtered and concentrated. The residue is,if appropriate, freed from any impurities that may still be presentusing customary methods, such as chromatography or recrystallization.

Chiral Compounds of the Formula (I-a)

To prepare chiral compounds of the formula (I-a), it is possible, forexample, to subject Δ¹-pyrrolines of the formula (II-b)

in whichR¹, R², R⁴ and m have the meanings given above,

-   Z⁴ represents chlorine, bromine or iodine    to an optical resolution. To this end, for example, methods of    preparative chromatography, preferably the high performance liquid    chromatography (HPLC) method, are employed. Here, a chiral    stationary silica gel phase is used. A    tris(3,5-dimethylphenylcarbamate)-cellulose-modified silica gel has    been found to be particularly suitable for separating the compounds    of the formula (II-b) into the two enantiomers. This separating    material is commercially available. However, it is also possible to    use other stationary phases. Suitable mobile phases are all    customary inert organic solvents, and mixtures of these. Preference    is given to using optionally halogenated aliphatic, alicyclic or    aromatic hydrocarbons, such as petroleum ether, hexane, heptane,    cyclohexane; dichloromethane, chloroform; alcohols, such as    methanol, ethanol, propanol; nitriles, such as acetonitrile; esters,    such as methyl acetate or ethyl acetate. Particular preference is    given to using aliphatic hydro-carbons, such as hexane or heptane,    and alcohols, such as methanol or propanol, very particularly    preferably n-heptane and isopropanol or mixtures of these. In    general, the separation is carried out at temperatures between    10° C. and 60° C., preferably between 10° C. and 40° C.,    particularly preferably at room temperature. The (R)-configured    enantiomers obtained in this manner are then used as starting    materials for the processes (A), (C) or (D).

When carrying out the processes (A), (B), (C) and (D) according to theinvention, in each case a palladium catalyst is employed, which for itspart can be used with or without addition of further ligands. Thecatalyst used is preferably PdCl₂(dppf)[dppf=1,1′-bis(diphenylphosphino)ferrocene], Pd(PPh₃)₄, PdCl₂(PPh₃)₂,PdCl₂(CH₃CN)₂, Pd₂(dba)₃ [dba=dibenzylideneacetone] or Pd(OAc)₂,particularly preferably PdCl₂(dppf), Pd(PPh₃)₄, PdCl₂(PPh₃)₂ orPd(OAc)₂, very particularly preferably PdCl₂(dppf) or PdCl₂(PPh₃)₂.

Suitable ligands are triarylphosphines, trialkylphosphines or arsines.Preference is given to using dppf, PPh₃, P(t-Bu)₃, Pcy₃ or AsPh₃,particularly preferably dppf.

Suitable diluents for carrying out the processes (A), (B) and (C)according to the invention are in each case all customary inert organicsolvents. Preference is given to using optionally halogenated aliphatic,alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane,heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene ordecalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform,tetrachloromethane, dichlorethane or trichloroethane; ethers, such asdiethyl ether, diisopropyl ether, methyl tert-butyl ether, methyltert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; nitriles, such as acetonitrile,propionitrile, n- or isobutyronitrile or benzonitrile; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such asmethyl acetate or ethyl acetate, sulphoxides, such as dimethylsulphoxide, or sulphones, such as sulpholane. Particular preference isgiven to using acetone, dimethoxyethane, dioxane, tetrahydrofuran,dimethylformamide, dimethylacetamide, dimethyl sulphoxide, ethanol,toluene or, if appropriate, mixtures of the diluents mentioned withwater.

Suitable diluents for carrying out the processes (D) and (E) accordingto the invention are in each case all customary inert organic solvents.Preference is given to using optionally halogenated aliphatic, alicyclicor aromatic hydrocarbons, such as petroleum ether, hexane, heptane,cyclohexane, methylcyclohexane, benzene, toluene, xylene or decaline;chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbontetrachloride, dichlorethane or trichloroethane; ethers, such as diethylether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amylether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethaneor anisole. Particular preference when carrying out process (D)according to the invention is given to using dioxane, tetrahydrofuran ortoluene.

Suitable acid binders for carrying out the processes (A), (B), (C) and(D) according to the invention are in each case all inorganic andorganic bases which are customary for such reactions. Preference isgiven to using alkaline earth metal or alkali metal hydroxides, such assodium hydroxide, calcium hydroxide, potassium hydroxide, or elseammonium hydroxide, alkali metal carbonates, such as sodium carbonate,potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkalimetal or alkaline earth metal acetates, such as sodium acetate,potassium acetate, calcium acetate, alkali metal fluorides, and alsotertiary amines, such as trimethylamine, triethylamine, tributylamine,N,N-dimethylaniline, pyridine, N-methylpiperidine,N,N-dimethylaminopyridine, diazabicyclooctane (DABCO),diazabicyclononene (DBN) or diazabicycloundecene (DBU). However, it isalso possible to operate without additional acid binder, or to employ anexcess of the amine component, so that it simultaneously acts as acidbinder. Barium hydroxide, sodium hydroxide, potassium hydroxide,tripotassium phosphate, caesium carbonate, potassium carbonate, sodiumcarbonate, potassium acetate, triethylamine, potassium tert-butoxide,caesium fluoride or potassium fluoride are used with particularpreference.

Suitable acid binders for carrying out the process (E) according to theinvention are in each case all inorganic and organic bases which arecustomary for such reactions. Preference is given to using alkali metalcarbonates, such as sodium carbonate, potassium carbonate, potassiumbicarbonate, sodium bicarbonate, and also tertiary amines, such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,pyridine, N-methylpiperidine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU). However, it is also possible to operatewithout additional acid binder.

When carrying out the processes (A), (B) and (C) according to theinvention, the reaction temperatures can in each case be varied within arelatively wide range. In general, the reactions are carried out attemperatures between 0° C. and 140° C., preferably between 20° C. and120° C., particularly preferably between 60° C. and 100° C.

When carrying out the process (D) according to the invention, thereaction temperatures can in each case be varied within a relativelywide range. In general, the reaction is carried out at temperaturesbetween 0° C. and 140° C., preferably between 20° C. and 120° C.

When carrying out the process (E) according to the invention, thereaction temperatures can in each case be varied within a relativelywide range. In general, the reaction is carried out at temperaturesbetween 0° C. and 100° C., preferably between 20° C. and 50° C.

All processes according to the invention are generally carried out underatmospheric pressure. However, in each case it is also possible tooperate under elevated or reduced pressure.

The active compounds according to the invention are suitable forcontrolling animal pests, in particular insects, arachnids andnematodes, which are encountered in agriculture, in forestry, in theprotection of stored products and of materials, and in the hygienesector, and have good plant tolerance and favourable toxicity towarm-blooded animals. They may be preferably employed as plantprotection agents. They are active against normally sensitive andresistant species and against all or some stages of development. Theabovementioned pests include:

-   From the order of the Isopoda, for example, Oniscus asellus,    Armadillidium vulgare and Porcellio scaber.-   From the order of the Diplopoda, for example, Blaniulus guttulatus.-   From the order of the Chilopoda, for example, Geophilus carpophagus    and Scutigera spp.-   From the order of the Symphyla, for example, Scutigerella    immaculata.-   From the order of the Thysanura, for example, Lepisma saccharina.-   From the order of the Collembola, for example, Onychiurus armatus.-   From the order of the Orthoptera, for example, Acheta domesticus,    Gryllotalpa spp., Locusta migratoria inigratorioides, Melanoplus    spp. and Schistocerca gregaria.-   From the order of the Blattaria, for example, Blatta orientalis,    Periplaneta americana, Leucophaea maderae and Blattella germanica.-   From the order of the Dermaptera, for example, Forficula    auricularia.-   From the order of the Isoptera, for example, Reticulitermes spp.-   From the order of the Phthiraptera, for example, Pediculus humanus    corporis, Haematopinus spp., Linognathus spp., Trichodectes spp. and    Damalinia spp.-   From the order of the Thysanoptera, for example, Hercinothrips    femoralis, Thrips tabaci, Tbrips palmi and Frankliniella    accidentalis.-   From the order of the Heteroptera, for example, Eurygaster spp.,    Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius    prolixus and Triatoma spp.-   From the order of the Homoptera, for example, Aleurodes brassicae,    Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,    Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi,    Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix,    Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli,    Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix    cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus,    Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,    Pseudococcus spp. and Psylla spp.-   From the order of the Lepidoptera, for example, Pectinophora    gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis    blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma    neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix    thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp.,    Feltia spp., Earias insulana, Heliothis spp., Mamestra brassicae,    Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa    pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia    kuehniella, Galleria mellonella, Tineola bisselliella, Tinea    pellionella, Hofinannophila pseudospretella, Cacoecia podana, Capua    reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona    magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.-   From the order of the Coleoptera, for example, Anobium punctatum,    Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,    Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata,    Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala,    Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis,    Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus,    Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica,    Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp.,    Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus,    Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp.,    Conoderus spp., Melolontha melolontha, Amphimallon solstitialis,    Costelytra zealandica and Lissorhoptrus oryzophilus.-   From the order of the Hymenoptera, for example, Diprion spp.,    Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.-   From the order of the Diptera, for example, Aedes spp., Anopheles    spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp.,    Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra    spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus    spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus,    Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis    capitata, Dacus oleae, Tipula paludosa, Hylemyia spp. and Liriomyza    spp.-   From the order of the Siphonaptera, for example, Xenopsylla cheopis    and Ceratophyllus spp.-   From the class of the Arachnida, for example, Scorpio maurus,    Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,    Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,    Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,    Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,    Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus    spp., Hemitarsonemus spp., Brevipalpus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

In particular, the compounds of the formula (I) according to theinvention have excellent activity against caterpillars, beetle larvae,spider mites, aphids and leaf-mining flies.

If appropriate, the compounds according to the invention can, at certainconcentrations or application rates, also be used as herbicides ormicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they can also be employed as intermediates or precursorsfor the synthesis of other active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (including naturally occurring crop plants). Cropplants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, including the transgenicplants and including the plant cultivars protectable or not protectableby plant breeders' rights. Plant parts are to be understood as meaningall parts and organs of plants above and below the ground, such asshoot, leaf, flower and root, examples which may be mentioned beingleaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds,roots, tubers and rhizomes. The plant parts also include harvestedmaterial, and vegetative and generative propagation material, forexample cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

The active compounds according to the invention can be converted intothe customary formulations, such as solutions, emulsions, wettablepowders, suspensions, powders, dusts, pastes, soluble powders, granules,suspension-emulsion concentrates, natural and synthetic materialsimpregnated with active compound and microencapsulations in polymericsubstances.

These formulations are produced in a known manner, for example by mixingthe active compounds according to the invention with extenders, that isliquid solvents and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as highly disperse silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, and also synthetic granules of inorganicand organic meals, and granules of organic material such as sawdust,coconut shells, maize cobs and tobacco stalks;

suitable emulsifiers and/or foam-formers are: for example nonionic andanionic emulsifiers, such as polyoxyethylene fatty acid esters,polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, alkyl sulphates, arylsulphonates and alsoprotein hydrolysates;

-   suitable dispersants are: for example lignosulphite waste liquors    and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used in customarycommercial form or in their formulations as a mixture with other activecompounds, such as insecticides, attractants, sterilizing agents,bactericides, acaricides, nematicides, fungicides, growth-regulatingsubstances or herbicides. The insecticides include, for example,phosphoric acid esters, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas and substances produced by microorganisms,inter alia.

Particularly advantageous co-components are, for example, the following:

Fungicides:

-   aldimorph, ampropylfos, ampropylfos-potassium, andoprim, anilazine,    azaconazole, azoxystrobin,-   benalaxyl, benodanil, benomyl, benzamacril, benzamacryl-isobutyl,    bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,    bromuconazole, bupirimate, buthiobate,-   calcium polysulphide, capsimycin, captafol, captan, carbendazim,    carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,    chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,    cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,-   debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,    dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,    diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,    ditalimfos, dithianon, dodemorph, dodine, drazoxolon,-   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,-   famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,    fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,    fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover,    fluoromide, fluquinconazole, flurprimidol, flusilazole,    flusulphamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,    fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,    furcarbonil, furconazole, furconazole-cis, furmecyclox, guazatine,    hexachlorobenzene, hexaconazole, hymexazole,-   imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,    iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),    iprodione, irunamycin, isoprothiolane, isovaledione,-   kasugamycin, kresoxim-methyl, copper preparations, such as: copper    hydroxide, copper naphthenate, copper oxychloride, copper sulphate,    copper oxide, oxine-copper and Bordeaux mixture,-   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,    metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,    metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,-   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,-   ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,    oxyfenthiin,-   paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,    pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,    procymidone, propamocarb, propanosine-sodium, propiconazole,    propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,    pyroxyfur,-   quinconazole, quintozene (PCNB),-   sulphur and sulphur preparations,-   tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,    thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,    tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,    triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,    triflumizole, triforine, triticonazole,-   uniconazole,-   validamycin A, vinclozolin, viniconazole,-   zarilamide, zineb, ziram and also-   Dagger G, OK-8705, OK-8801,-   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,-   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,-   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,-   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,-   1-isopropyl    {2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,-   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,-   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,-   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,-   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,-   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,-   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,-   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,-   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,-   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide,-   2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,-   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,-   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,-   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,-   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,-   2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,-   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucpyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,-   2-aminobutane,-   2-bromo-2-(bromomethyl)-pentanedinitrile,-   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,-   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,-   2-phenylphenol (OPP),-   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,-   3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,-   3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,-   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,-   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,-   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,-   8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4,5]decane-2-methanamine,-   8-hydroxyquinoline sulphate,-   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,-   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,-   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,-   cis-4-[3-[4-(1,1-dimethylpropyl]-phenyl-2-methylpropyl]-2,6-dimethylmorpholine    hydrochloride,-   ethyl [(4-chlorophenyl)-azo]-cyanoacetate,-   potassium bicarbonate,-   methanetetrathiol-sodium salt,-   methyl    1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,-   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,-   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,-   N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,-   N-(2-chloro-4-nitrophenyl)4-methyl-3-nitro-benzenesulphonamide,-   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,-   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,-   N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide,-   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,-   N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,-   N-formyl-N-hydroxy-DL-alanine-sodium salt,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   O-methyl S-phenyl phenylpropylphosphoramidothioate,-   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,-   spiro[2H]-1-benzopyran-2,1′(3′H)-isobenzofuran-3′-one    Bactericides:-   bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,    kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,    probenazole, streptomycin, tecloftalam, copper sulphate and other    copper preparations.    Insecticides/Acaricides/Nematicides:-   abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,    aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin,    AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M,    azocyclotin,-   Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus    thuringiensis, baculoviruses, Beauveria bassiana, Beauveria tenella,    bendiocarb, benfuracarb, bensultap, benzoximate, betacyfluthrin,    bifenazate, bifenthrin, bioethanomethrin, biopermethrin, BPMC,    bromophos A, bufencarb, buprofezin, butathiofos, butocarboxim,    butylpyridaben,-   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan,    cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,    chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,    chlovaporthrin, cis-resmethrin, cispermethrin, clocythrin,    cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin,    cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,-   deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,    diazinon, dichlorvos, diflubenzuron, dimethoate, dimethylvinphos,    diofenolan, disulfoton, docusat-sodium, dofenapyn,-   eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,    eprinomectin, esfenvalerate, ethiofencarb, ethion, ethoprophos,    etofenprox, etoxazole, etrimfos,-   fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,    fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin,. fenpyrad,    fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazuron,    flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,    flutenzine, fluvalinate, fonophos, fosmethilan, fosthiazate,    fubfenprox, furathiocarb,-   granulosis viruses,-   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,    hydroprene,-   imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,-   nuclear polyhedrosis viruses,-   lambda-cyhalothrin, lufenuron,-   malathion, mecarbam, metaldehyde, methamidophos, Metharhizium    anisopliae, Metharhizium flavoviride, methidathion, methiocarb,    methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,    milbemectin, monocrotophos,-   naled, nitenpyram, nithiazine, novaluron,-   omethoate, oxamyl, oxydemethon M,-   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,    phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,    pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,    propoxur, prothiofos, prothoate, pymetrozine, pyraclofos,    pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,    pyriproxyfen,-   quinalphos,-   ribavirin,-   salithion, sebufos, selamectin, silafluofen, spinosad, sulphotep,    sulprofos,-   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,    teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,    tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil,    thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,    thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,    triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron,    trimethacarb,-   vamidothion, vaniliprole, Verticillium lecanii,-   YI 5302,-   zeta-cypermethrin, zolaprofos,-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,-   (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate,-   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,-   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,-   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,-   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   3-methylphenyl propylcarbamate.-   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,-   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,-   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,-   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,-   Bacillus thuringiensis strain EG-2348,-   [2-benzoyl-1-(1,1-dimethylethyl]-hydrazinobenzoic acid,-   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl    butanoate,-   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,-   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,-   ethyl    [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,-   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,-   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,-   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N″-nitro-guanidine,-   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,-   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,-   O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate

It is also possible to admix other known active compounds, such asherbicides, fertilizers and growth regulators.

When used as insecticides, the active compounds according to theinvention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergistic agents. Synergistic agents are compoundswhich increase the action of the active compounds according to theinvention, without it being necessary for the synergistic agent added tobe active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars (i.e. those obtainedby genetic engineering) which are to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparted particular advantageous usefulproperties (“traits”) to these plants. Examples of such properties arebetter plant growth, increased tolerance to high or low temperatures,increased tolerance to drought or to water or soil salt content,increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products. Further andparticularly emphasized examples of such properties are a better defenceof the plants against animal and microbial pests, such as againstinsects, mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, cotton, oilseed rape and also fruit plants (with the fruitsapples, pears, citrus fruits and grapevines), and particular emphasis isgiven to maize, soya beans, potatoes, cotton and oilseed rape. Traitsthat are emphasized are in particular increased defence of the plantsagainst insects by toxins formed in the plants, in particular thoseformed by the genetic material from Bacillus thuringiensis (for exampleby the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2,Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof)(hereinbelow referred to as “Bt plants”). Traits that are furthermoreparticularly emphasized are the increased tolerance of the plants tocertain herbicidally active compounds, for example imidazolinones,sulphonylureas, glyphosate or phosphinotricin (for example the “PAT”gene). The genes which impart the desired traits in question can also bepresent in combination with one another in the transgenic plants.Examples of “Bt plants” which may be mentioned are maize varieties,cotton varieties, soya bean varieties and potato varieties which aresold under the trade names YIELD GARD® (for example maize, cotton, soyabeans), KnockOut® (for example maize), StarLink® (for example maize),Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples ofherbicide-tolerant plants which may be mentioned are maize varieties,cotton varieties and soya bean varieties which are sold under the tradenames Roundup Ready® (tolerance to glyphosate, for example maize,cotton, soya bean), Liberty Link® ((tolerance to phosphinotricin, forexample oilseed rape), IMI® (tolerance to imidazolinones) and STS®(tolerance to sulphonylureas, for example maize). Herbicide-resistantplants (plants bred in a conventional manner for herbicide tolerance)which may be mentioned include the varieties sold under the nameClearfield® (for example maize). Of course, these statements also applyto plant cultivars having these or still to be developed genetic traits,which plants will be developed and/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) or the active compound mixtures according to the invention.The preferred ranges stated above for the active compounds or mixturesalso apply to the treatment of these plants. Particular emphasis isgiven to the treatment of plants with the compounds or the mixturesspecifically mentioned in the present text.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

-   From the order of the Anoplurida, for example, Haematopinus spp.,    Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.-   From the order of the Mallophagida and the suborders Amblycerina and    Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton    spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina    spp., Trichodectes spp. and Felicola spp.-   From the order of the Diptera and the suborders Nematocerina and    Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,    Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,    Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp.,    Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca    spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp.,    Fannia spp., Glossina spp., Calliphora spp., Lucilia spp.,    Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp.,    Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp.    and Melophagus spp.-   From the order of the Siphonapterida, for example, Pulex spp.,    Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.-   From the order of the Heteropterida, for example, Cimex spp.,    Triatoma spp., Rhodnius spp. and Panstrongylus spp.-   From the order of the Blattarida, for example, Blatta orientalis,    Periplaneta americana, Blattella germanica and Supella spp.-   From the subclass of the Acaria (Acarida) and the orders of the    Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp.,    Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,    Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus    spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp.,    Stemostoma spp. and Varroa spp.-   From the order of the Actinedida (Prostigmata) und Acaridida    (Astigmata), for example, Acarapis spp., Cheyletiella spp.,    Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,    Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,    Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,    Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,    Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

They have, for example, excellent activity against the developmentstages of ticks such as, for example, Amblyomma hebraeum, againstparasitic flies such as, for example, Lucilia cuprina and against fleassuch as, for example, Ctenocephalides felis.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injection(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) according to the invention can be used asformulations (for example powders, emulsions, free-flowingcompositions), which comprise the active compounds according to theinvention in an amount of 1 to 80% by weight, directly or after 100 to10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as preferred—butwithout a limitation:

Beetles, such as

-   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,    Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex,    Emobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus,    Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon    aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec.,    Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,    Sinoxylon spec., Dinoderus minutus.

Hymenopterons, such as

-   Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus    augur.

Termites, such as

-   Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,    Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes    lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,    Coptotermes formosanus.

Bristletails, such as Lepisma saccarina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentsaccording to the invention or mixtures comprising these are to beunderstood as meaning, for example:

-   building timber, wooden beams, railway sleepers, bridge components,    boat jetties, wooden vehicles, boxes, pallets, containers, telegraph    poles, wood panelling, wooden window frames and doors, plywood,    chipboard, joinery or wooden products which are used quite generally    in house-building or in building joinery.

The active compounds according to the invention can be used as such, inthe form of concentrates or in generally customary formulations, such aspowders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds according to the invention withat least one solvent or diluent, emulsifier, dispersing agent and/orbinder or fixing agent, a water repellent, if appropriate siccatives andUV stabilizers and if appropriate dyestuffs and pigments, and also otherprocessing auxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by series oftests. In general, however, it is sufficient to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound, basedon the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., terpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablya-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, provided that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by an aliphatic polar organicchemical solvent or solvent mixture. Aliphatic organic chemical solventscontaining hydroxyl and/or ester and/or ether groups, such as, forexample, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-coumaroneresin, silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or a drying vegetable oil. Alkydresins having an oil content of more than 45% by weight, preferably 50to 68% by weight, are preferably used according to the invention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, delta-methrin, permethrin, imidacloprid,NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid,methoxyfenozide and triflumuron, and also fungicides, such asepoxy-conazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with saltwateror brackish water, such as hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance.

Surprisingly, it has now been found that the compounds according to theinvention, alone or in combination with other active compounds, have anoutstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthio-carbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

algicides such as

-   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,    dichlorophen, diuron, endothal, fentin acetate, isoproturon,    methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;

fungicides such as

-   benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,    dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,    tolylfluanid and azoles such as azaconazole, cyproconazole,    epoxyconazole, hexaconazole, metconazole, propiconazole and    tebuconazole;

molluscicides such as

-   fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and    trimethacarb;

or conventional antifouling active compounds such as

-   4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl    sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,    potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,    pyridine-triphenylborane, tetrabutyldistannoxane,    2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,    2,4,5,6-tetrachloroisophthalonitrile, tetra-methylthiuram disulphide    and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730–732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds according to the invention are also suitable forcontrolling animal pests, in particular insects, arachnids and mites,which are found in enclosed spaces such as, for example, dwellings,factory halls, offices, vehicle cabins and the like. They can beemployed alone or in combination with other active compounds andauxiliaries in domestic insecticide products for controlling thesepests. They are active against sensitive and resistant species andagainst all development stages. These pests include:

-   From the order of the Scorpionidea, for example, Buthus occitanus.-   From the order of the Acarina, for example, Argas persicus, Argas    reflexus, Bryobia spp., Dermanyssus gallinae, Glyciphagus    domesticus, Omithodorus moubat, Rhipicephalus sanguineus, Trombicula    alfreddugesi, Neutrombicula autumnalis, Dermatophagoides    pteronissimus and Dermatophagoides forinae.-   From the order of the Araneae, for example, Aviculariidae and    Araneidae.-   From the order of the Opiliones, for example, Pseudoscorpiones    chelifer, Pseudoscorpiones cheiridium and Opiliones phalangium.-   From the order of the Isopoda, for example, Oniscus asellus and    Porcellio scaber.-   From the order of the Diplopoda, for example, Blaniulus guttulatus    and Polydesmus spp.-   From the order of the Chilopoda, for example, Geophilus spp.-   From the order of the Zygentoma, for example, Ctenolepisma spp.,    Lepisma saccharina and Lepismodes inquilinus.-   From the order of the Blattaria, for example, Blatta orientalies,    Blattella germanica, Blattella asahinai, Leucophaea maderae,    Panchlora spp., Parcoblatta spp., Periplaneta australasiae,    Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa    and Supella longipalpa.-   From the order of the Saltatoria, for example, Acheta domesticus.-   From the order of the Dermaptera, for example, Forficula    auricularia.-   From the order of the Isoptera, for example, Kalotermes spp. and    Reticulitermes spp.-   From the order of the Psocoptera, for example, Lepinatus spp. and    Liposcelis spp.-   From the order of the Coleptera, for example, Anthrenus spp.,    Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp.,    Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus    oryzae, Sitophilus zeamais and Stegobium paniceum.-   From the order of the Diptera, for example, Aedes aegypti, Aedes    albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora    erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex    pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca    domestica, Phlebotomus spp., Sarcophaga camaria, Simulium spp.,    Stomoxys calcitrans and Tipula paludosa.-   From the order of the Lepidoptera, for example, Achroia grisella,    Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea    pellionella and Tineola bisselliella.-   From the order of the Siphonaptera, for example, Ctenocephalides    canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans and    Xenopsylla cheopis.-   From the order of the Hymenoptera, for example, Camponotus    herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,    Monomorium pharaonis, Paravespula spp. and Tetramorium caespitum.-   From the order of the Anoplura, for example, Pediculus humanus    capitis, Pediculus humanus corporis and Phthirus pubis.-   From the order of the Heteroptera, for example, Cimex hemipterus,    Cimex lectularius, Rhodinus prolixus and Triatoma infestans.

In the field of household insecticides, they are used alone or incombination with other suitable active compounds, such as phosphoricacid esters, carbamates, pyrethroids, growth regulators or activecompounds from other known classes of insecticides.

They are used as aerosols, unpressurized spray products, for examplepump and atomizer sprays, automatic misting systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

The preparation and use of the substances according to the invention isshown in the examples below.

PREPARATION EXAMPLES Example 1

5-(2,6-Difluorophenyl)-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3,4-dihydro-2H-pyrrole(0.96 g, 2.50 mmol) is dissolved in 10 ml of N,N-dimethylacetamide.Methyl 4-bromophenylcarbamate (III-1) (0.69 g, 3.00 mmol), PdCl₂[dppf](0.05 g, 0.07 mmol) and 3.75 ml of sodium carbonate solution (2 M) areadded in succession and the mixture is subsequently stirred at 80° C.for 16 h. It is cooled to room temperature and extracted withwater/ethyl acetate and the organic phase is separated off, dried overmagnesium sulphate, filtered and concentrated under reduced pressure.The crude product is purified by silica gel chromatography(cyclohexane/ethyl acetate 91:9→80:20, each v/v).

This gives 0.35 g (32% of theory) of methyl4′-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]-1,1′-biphenyl-4-ylcarbamate.

HPLC: log P (pH 2.3)=2.31 (purity: 93%)

-   -   log P (pH 7.5)=3.52

Example 2

5-(2,6-Difluorophenyl)-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3,4-dihydro-2H-pyrrole(0.96 g, 2.50 mmol) and n-propyl 4-bromophenylcarbamate (III-2) (0.77 g,3.00 mmol) are dissolved in 10 ml of 1,2-dimethoxyethane. PdCl₂[dppf](0.05 g, 0.07 mmol) and 3.75 ml of sodium carbonate solution (2 M) areadded in succession and the mixture is subsequently stirred at 80° C.for 16 h. It is cooled to room temperature and extracted withwater/ethyl acetate and the organic phase is separated off, dried overmagnesium sulphate, filtered and concentrated under reduced pressure.The crude product is purified by silica gel chromatography(cyclohexane/ethyl acetate 20:1→6:1→2:1, each v/v).

This gives 0.28 g (25% of theory) of n-propyl4′-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]-1,1′-biphenyl-4-ylcarbamate.

HPLC: log P (pH 2.3)=3.02 (purity: 98%)

-   -   log P (pH 7.5)=4.24

Example 3

5-(2,6-Difluorophenyl)-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3,4-dihydro-2H-pyrrole(0.96 g, 2.50 mmol) is dissolved in 20 ml of N,N-dimethylacetamide.n-Butyl 4-bromophenyl(methyl)carbamate (III-3) (0.86 g, 3.00 mmol),PdCl₂[dppf] (0.05 g, 0.07 mmol) and 3.75 ml of sodium carbonate solution(2 M) are added in succession and the mixture is subsequently stirred at90° C. for 16 h. It is cooled to room temperature and the reactionmixture is concentrated under reduced pressure. The residue is taken upin ethyl acetate and washed with water. The organic phase is separatedoff, dried over magnesium sulphate, filtered and concentrated underreduced pressure. The crude product is purified by silica gelchromatography (cyclohexane/ethyl acetate 10:1→6:1, each v/v).

This gives 0.48 g (41% of theory) of n-butyl4′-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]-1,1′-biphenyl-4-yl(methyl)carbamate.

HPLC: log P (pH 2.3)=3.76 (purity: 98%)

-   -   log P (pH 7.5)=4.92

Example 4

5-(2,6-Difluorophenyl)-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3,4-dihydro-2H-pyrrole(0.96 g, 2.50 mmol) is dissolved in 20 ml of N,N-dimethylacetamide.3-(4-Bromophenyl)-1,3-oxazolidin-2-one (III-4) (0.73 g, 3.00 mmol),PdCl₂[dppf] (0.05 g, 0.07 mmol) and 3.75 ml of sodium carbonate solution(2 M) are added in succession and the mixture is subsequently stirred at90° C. for 16 h. It is cooled to room temperature, water is added, andthe precipitate is filtered off with suction. The crude product ispurified by silica gel chromatography (cyclohexane/acetone 20:1→10:1,each v/v).

This gives 0.75 g (66% of theory) of3-{4′-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]-1,1′-biphenyl-4-yl}-1,3-oxazolidin-2-one.

HPLC: log P (pH 2.3)=2.13 (purity: 92%)

-   -   log P (pH 7.5)=3.28

Example 5

5-(2,6-Difluorophenyl)-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3,4-dihydro-2H-pyrrole(0.96 g, 2.50 mmol) and N-(4-bromophenyl)-4-morpholine-carboxamide(III-5) (0.86 g, 3.00 mmol) are dissolved in 10 ml of1,2-dimethoxyethane. PdCl₂[dppf] (0.05 g, 0.07 mmol) and 3.75 ml ofsodium carbonate solution (2 M) are added in succession and the mixtureis subsequently stirred at 80° C. for 16 h. It is cooled to roomtemperature and extracted with water/ethyl acetate and the organic phaseis separated off, dried over magnesium sulphate, filtered andconcentrated under reduced pressure. The crude product is purified bysilica gel chromatography (cyclohexane/ethyl acetate 2:1→1:1, each v/v).

This gives 0.35 g (30% of theory) ofN-{4′-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol -2-yl]-1,1′-biphenyl-4-yl}-4-morpholinecarboxamide.

HPLC: log P (pH 2.3)=1.87 (purity: 100%)

-   -   log P (pH 7.5)=2.96

In analogy to Examples 1 to 5 above and in accordance with the generalpreparation details, the compounds of the formula (I) indicated in thefollowing table are obtained.

(I)

No. R¹ R² R⁴ _(m) —A—R³ log P  6 F F —

2.62^(a))3.85^(b))  7 F F —

3.00^(a))4.19^(b))  8 F F —

3.32^(a))4.54^(b))  9 F F —

3.44^(a))4.60^(b)) 10 F F —

3.88^(a))1.68^(b)) 11 F F —

2.11^(a)) 12 F F —

2.53^(a))3.71^(b)) 13 F F —

1.71^(a))2.78^(b)) 14 F F —

3.18^(a))4.36^(b)) 15 F F —

2.48^(a))3.47^(b)) 16 F F —

3.82^(a))4.77^(b)) 17 F F —

4.82^(b)) 18 F F —

3.87^(a))4.89^(b)) 19 F F —

4.46^(a))5.26^(b)) 20 F F —

3.63^(a)) 21 F F —

3.72^(a)) 22 F F —

2.71^(a))3.98^(b)) 23 F F —

3.76^(a)) 24 F F —

3.76^(a)) 25 F F —

3.62^(a))4.64^(b)) 26 F F —

3.01^(a))4.10^(b)) 27 F F —

3.28^(a))4.36^(b)) 28 F F —

5.13^(a))5.97^(b)) 29 F F —

1.74^(a))5.52^(b)) 30 F F —

1.37^(a)) 31 F F —

2.24^(a))3.45^(b)) 32 F F —

2.52^(a))3.75^(b)) 33 F F —

3.82^(a)) 34 F F —

3.70^(a))4.73^(b)) 35 F F —

2.58^(a))3.79^(b)) 36 F F —

3.32^(a))4.52^(b)) 37 F F —

2.92^(a))4.16^(b)) 38 F F —

2.40^(a)) 39 F F —

4.11^(a))5.19^(b)) 40 F F —

3.30^(a))4.50^(b)) 41 F F —

3.79^(a))4.89^(b)) 42 F F —

2.54^(a))3.88^(b))Preparation of Starting Materials of the Formula (III)

Example (III-1)

A solution of 4-bromophenyl isocyanate (3.26 g, 16.46 mmol) in 15 ml oftoluene is added dropwise at room temperature to 1 ml of methanol and 20ml of toluene and the mixture is stirred at room temperature for afurther 16 hours. The reaction mixture is concentrated under reducedpressure. The crude product is purified by silica gel chromatography(cyclohexane/ethyl acetate 2:1, v/v).

This gives 3.65 g (88% of theory) of methyl 4-bromophenylcarbamate.

HPLC: log P (pH 2.3)=2.27 (purity: 92%)

Example (III-2)

1.85 ml of n-propanol is introduced in 10 ml of toluene under an argonatmosphere. 4-Bromophenyl isocyanate (3.26 g, 16.46 mmol) is added inportions at room temperature and the reaction mixture is stirred at roomtemperature for a further 16 hours. The reaction mixture is concentratedunder reduced pressure. The crude product is purified by silica gelchromatography (cyclohexane/ethyl acetate 2:1, v/v).

This gives 4.13 g (95% of theory) of n-propyl 4-bromophenylcarbamate.

HPLC: log P (pH 2.3)=3.12 (purity: 98%)

Example (III-3)

N-(4-Bromophenyl)-N-methylamine (1.50 g, 8.06 mmol) is introduced in 15ml of dichloromethane under an argon atmosphere and thenN,O-bis(trimethylsilyl)-acetamide (1.97 g, 9.67 mmol) is added and themixture is stirred at room temperature for 1 hour. It is then cooled to0° C. and butyl chloroformate (1.23 ml, 9.67 mmol) is added dropwise.The mixture is warmed to room temperature and stirred at thistemperature for a further 16 hours. It is cooled again to 0° C.,quenched with potassium dihydrogen phosphate/disodium hydrogen phosphatebuffer pH 7 and extracted with dichloromethane and the organic phase isseparated off, washed with saturated sodium chloride solution, driedover magnesium sulphate, filtered and concentrated under reducedpressure.

This gives 1.13 g (98% of theory) ofn-butyl-4-bromophenyl(methyl)carbamate.

HPLC: log P (pH 2.3) 3.88 (purity: 96%)

Example (III-4)

4-Bromophenyl isocyanate (2.00 g, 10.10 mmol) is introduced in 15 ml ofdimethyl sulphoxide under an argon atmosphere and then dioxolan-2-one(0.89 g, 10.10 mmol) and caesium fluoride (0.15 g, 1.01 mmol) are added,whereupon a white precipitate is formed. The mixture is stirred at 140°C. under argon for 2 hours. The reaction mixture is cooled and pouredinto ice-water and the precipitate formed is filtered off with suction,dried and recrystallized from isopropanol.

This gives 1.55 g (61% of theory) of3-(4-bromophenyl)-1,3-oxazolidin-2-one.

HPLC: log P (pH 2.3)=2.02 (purity: 96%)

Example (III-5)

1.96 ml of morpholine is introduced in 15 ml of dioxane under an argonatmosphere. At room temperature, 4-bromophenyl isocyanate (2.97 g, 15.00mmol) is added in portions and the reaction mixture is stirred at roomtemperature for a further 16 hours. The crude product is subsequentlyfiltered off with suction and isolated by silica gel chromatography(cyclohexane/ethyl acetate 2:1, v/v).

This gives 3.13 g (66% of theory) ofN-(4-bromophenyl)-4-morpholinecarboxamide.

HPLC: log P (pH 2.3)=1.75 (purity: 91%)

Preparation of Starting Materials of the Formula (VII)

Example (VII-1)

Methyl4′-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]-1,1′-biphenyl-4-yl-carbamate(Example 1) (0.23 g, 0.53 mmol) is dissolved in 2 ml of ethanol.Following addition of potassium hydroxide (0.03 g, 0.53 mmol) themixture is stirred under reflux for 16 hours. The precipitate isfiltered off with suction and the crude product is purified by silicagel chromatography (cyclohexane/ethyl acetate 2:1, v/v).

This gives 0.13 g (69% of theory) of4′-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]-1′-biphenyl-4-amine.

HPLC: log P (pH 2.3)=1.25 (purity: 97%)

The logP values stated in the above tables and Preparation Examples aredetermined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC(High Performance Liquid Chromatography) using a reversed-phase column(C 18). Temperature: 43° C.

In the acidic range at pH 2.3 the determination takes place using 0.1%aqueous phosphoric acid and acetonitrile as the mobile phases; lineargradient from 10% acetonitrile to 90% acetonitrile. Correspondingresults are marked in the tables by “a)”

In the neutral range at pH 7.5 the determination takes place using 0.01molar aqueous phosphate buffer solution and acetonitrile as the mobilephases; linear gradient from 10% acetonitrile to 90% acetonitrile.Corresponding results are marked in the tables by “b)”

Calibration is carried out using unbranched alkan-2-ones (having 3 to 16carbon atoms), with known logP values (the logP values determined on thebasis of the retention times using linear interpolation between twosuccessive alkanones).

Use Examples

Example A

Heliothis virescens Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Soya bean shoots (Glycine max) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with Heliothis virescens caterpillars whilst the leaves arestill moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

In this test, at an active compound concentration of 100 ppm, forexample, the compounds 2 and 6–8 from the Preparation Examples exhibit agood activity of at least 95%. The test results can be seen in detailfrom Table A below.

TABLE A Plant-damaging insects Heliothis virescens test Active compoundconcentration in Kill rate in % Active compounds ppm after 7^(d)

(6) 100 100

(2) 100 100

(7) 100 100

(8) 100 100

Example B

Phaedon larvae Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilstthe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae has been killed.

In this test, at an active compound concentration of 100 ppm, forexample, the compounds 1, 2, 6, 7, 16, 18–21, 24, 25, 27, 29, 32, 35, 37from the Preparation Examples exhibit a good activity of at least 85%.The test results can be seen in detail from Table B below.

TABLE B plant-damaging insects Phaedon larvae test Active compoundconcentration in Kill rate in % Active compounds ppm after 7^(d)

 (1) 100 100

 (6) 100 100

 (2) 100 100

 (7) 100 100

 (9) 100 100

(10) 100 100

(11) 100 100

(12) 100 100

(16) 100 100

(18) 100 100

(19) 100 100

(20) 100 100

(21) 100 100

(24) 100 100

(25) 100 100

(27) 100 100

(29) 100 100

(32) 100 100

(35) 100 100

(37) 100 90

Example C

Plutella Test, Sensitive Strain

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the cabbage moth (Plutella xylostella,sensitive strain) whilst the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

In this test, at an active compound concentration of 100 ppm, forexample, the compounds 2, 6–8 and 23 from the Preparation Examplesexhibit a good activity of at least 95%. The test results can be seen indetail from Table C below.

TABLE C plant-damaging insects Plutella test, sensitive strain Activecompound concentration in Kill rate in % Active compounds ppm after7^(d)

 (6) 100 100

 (2) 100 100

 (7) 100 100

 (8) 100 100

(23) 100 100

Example D

Plutella Test, Resistant Strain

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the cabbage moth (Plutella xylostella,sensitive strain) whilst the leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thebeetle larvae has been killed.

In this test, at an active compound concentration of 100 ppm, forexample, the compounds 2, 6–8 and 23 from the Preparation Examplesexhibit a good activity of at least 95%. The test results can be seen indetail from Table D below.

TABLE D plant-damaging insects Plutella test, resistant strain Activecompound concentration in Kill rate in % Active compounds ppm after7^(d)

 (6) 100 100

 (2) 100 100

 (7) 100 100

 (8) 100 100

(23) 100 100

Example E

Spodoptera exigua Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with army worm (Spodoptera exigua) caterpillars whilst theleaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

In this test, at an active compound concentration of 100 ppm, forexample, the compounds 2, 6–8 and 23 from the Preparation Examplesexhibit a good activity of at least 95%. The test results can be seen indetail from Table E below.

TABLE E plant-damaging insects Spodoptera exigua test Active compoundconcentration in Kill rate in % Active compounds ppm after 7^(d)

 (6) 100 100

 (2) 100 100

 (7) 100 100

 (8) 100 100

(23) 100 100

Example F

Spodoptera frugiperda Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with army worm (Spodoptera frugiperda) caterpillars whilst theleaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

In this test, at an active compound concentration of 100 ppm, forexample, the compounds 1, 2, 4–7, 9, 10, 12, 14, 17, 18, 20–23, 25–28,30, 31, 33, 34 and 37 from the Preparation Examples exhibit a goodactivity of at least 95%. The test results can be seen in detail fromTable F below.

TABLE F plant-damaging insects Spodoptera frugiperda-Test Activecompound concentration in Kill rate in % Active compounds ppm after7^(d)

 (1) 100 100

 (6) 100 100

 (2) 100 100

 (7) 100 100

 (9) 100 100

 (5) 100 100

(10) 100 100

(12) 100 100

(14) 100 100

(18) 100 100

(20) 100 100

(21) 100 100

(22) 100 100

(23) 100 100

(25) 100 100

(26) 100 100

(27) 100 100

(28) 100 100

(30) 100 100

(31) 100 100

(33) 100 100

(34) 100 100

(37) 100 100

 (4) 100 100

Example G

Tetranychus Test (OP Resistant/Dip Treatment)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by allstages of the greenhouse red spider mite (Tetranychus urticae) aredipped into a preparation of active compound of the desiredconcentration.

After the desired period of time, the effect in % is determined. 100%means that all spider mites have been killed; 0% means that none of thespider mites have been killed.

In this test, at an active compound concentration of 100 ppm, forexample, the compounds 1, 2, 4, 6, 7, 17, 19, 22–24, 26–30 und 32–35from the Preparation Examples exhibit a good activity of at least 85%.The test results can be seen in detail from Table G below.

TABLE G plant-damaging insects Tetranychus test (OP-resistant/diptreatment) Active compound concentration in Kill rate in % Activecompounds ppm after 7^(d)

 (1) 100 98

 (6) 100 98

 (2) 100 98

 (7) 100 98

(17) 100 90

(19) 100 90

(22) 100 90

(23) 100 95

(24) 100 95

(26) 100 98

(27) 100 98

(28) 100 95

(29) 100 98

(30) 100 95

(32) 100 98

(33) 100 100

(34) 100 90

(35) 100 98

 (4) 100 90

Example H

Diabrotica balteata Test (Larvae in Soil)

Critical Concentration Test/Soil Insects—Treatment of Transgenic Plants

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured onto the soil. Here, theconcentration of the active compound in the preparation is virtuallyimmaterial; only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l), matters. The soil is filled into0.25 l pots, and these are allowed to stand at 20° C.

Immediately after the preparation, 5 pregerminated maize corns of thecultivar YIELD GUARD (trade mark of Monsanto Comp., USA) are placed intoeach pot. After 2 days, the corresponding test insects are placed intothe treated soil. After a further 7 days, the efficacy of the activecompound is determined by counting the number of maize plants that haveemerged (1 plant=20% activity).

Example J

Heliothis virescens Test (Treatment of Transgenic Plants)

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soya bean shoots (Glycine max) of the cultivar Roundup Ready (trade markof Monsanto Comp. USA) are treated by being dipped into the preparationof active compound of the desired concentration and populated with thetobacco budworm caterpillar Heliothis virescens whilst the leaves arestill moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

Example K

Test with Boophilus microplus Resistant/SP-Resistant Parkhurst Strain

Test animals: Adult satiated females

Solvent: Dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide.Lower concentrations are prepared by dilution in the same solvent.

The test is carried out in 5 replications. 1 μl of the solutions isinjected into the abdomen, and the animals are transferred to dishes andkept in a climate-controlled room. After 7 days, activity is checked byexamination for deposition of fertile eggs. Eggs whose fertility is notexternally visible are stored in glass tubes in a controlled-environmentcabinet until the larvae have hatched. An activity of 100% denotes thatnone of the ticks has laid fertile eggs.

In this test, for example, the following compounds from the PreparationExamples exhibit very good activity:

TABLE K Test with Boophilus microplus resistant/SP-resistant Parkhurststrain Concentration in Activity/ Active compounds μg/animal kill in %

(6) 100/20   20/20  

(7) 100/20   40/0  

(8) 100/20/4 80/40/0

Example L

Test with Flies (Musca domestica)

Test animals: Adult Musca domestica, Reichswald strain (OP, SP,carbamate-resistant)

Solvent: Dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml dimethyl sulphoxide.Lower concentrations are prepared by dilution with distilled water.

2 ml of this active compound preparation are pipetted on filter paperdiscs (Ø9.5 cm) in Petri dishes of corresponding dimensions. After thefilter discs have been dried, 25 test animals are transferred to thePetri dishes, which are then covered.

After 1, 3, 5, 24 and 48 hours the activity of the active compoundpreparation is measured. 100% means that all flies have been killed, 0%means that no fly has been killed.

In this test, for example, the following compound from the PreparationExamples exhibits very good activity:

TABLE L Test mit Fliegen (Musca domestica) Concentration in Activity/Active compound ppm kill in %

(13) 100/20 30/0

1. A Δ¹-pyrroline of formula (I)

in which R¹ represents halogen or methyl, R² represents hydrogen orhalogen, R³ represents —N(R⁶)—C(═Y)—X—R⁷, A represents arylene that isoptionally substituted from one to four times by identical or differentsubstituents R⁵, Y represents O or S, X represents O, S, or NR⁸, R⁴ andR⁵ independently of one another represent halogen, alkyl, alkoxy,alkylthio, haloalkyl, haloalkoxy, or haloalkylthio, m represents 0, 1,2, 3, or 4, R⁶ represents hydrogen or alkyl, R⁷ and R⁸ independently ofone another represent hydrogen; represent alkyl or alkenyl, each ofwhich is optionally substituted one or more times by identical ordifferent substituents selected from the group consisting of halogen,alkylcarbonyl, alkylcarbonyloxy, alkylamino, dialkylamino, alkoxy,alkylthio, alkoxyalkoxy, haloalkoxy, haloalkylthio, andhalogenalkoxyalkoxy; or represent cycloalkyl, cycloalkylalkyl, aryl,arylalkyl, or saturated or unsaturated 5- to 10-membered heterocyclyl orheterocyclylalkyl, each of which is optionally substituted one or moretimes by identical or different substitutents selected from the groupconsisting of halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio,haloalkylthio, alkylcarbonyl, and alkoxycarbonyl, or R⁶ and R⁷ togetherrepresent alkylene optionally substituted one or more times by alkyl, orR⁷ and R⁸, together with the nitrogen atom to which they are attached,represent a saturated or unsaturated 5- to 10-membered heterocycle thatoptionally contains a further heteroatom group selected from the series—O—, —S—, and —NR⁹— and that is optionally substituted one or more timesby identical or different substituents selected from the groupconsisting of halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy,and haloalkylthio, and R⁹ represents hydrogen, alkyl, or alkenyl.
 2. AΔ¹-pyrroline of formula (I) according to claim 1 in which R¹ representsfluorine, chlorine, bromine, or methyl, R² represents hydrogen,fluorine, chlorine, or bromine, R³ represents —N(R⁶)—C(═Y)—X—R⁷, Arepresents arylene that is optionally substituted from one to threetimes by identical or different substituents R⁵, Y represents O or S, Xrepresents O, S, or NR⁸, R⁴ and R⁵ independently of one anotherrepresent fluorine, chlorine, bromine, C₁–C₆-alkyl, C₁–C₆-alkoxy,C₁–C₆-alkylthio, C₁–C₆-haloalkyl, C₁–C₆-haloalkoxy, orC₁–C₆-haloalkylthio, m represents 0, 1, 2, or 3, R⁶ represents hydrogenor C₁–C₆-alkyl, R⁷ and R⁸ independently of one another representhydrogen; represent C₁–C₂₀-alkyl or C₂–C₂₀-alkenyl, each of which isoptionally substituted one or more times by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, C₁–C₆-alkylcarbonyl, C₁–C₆-alkylcarbonyloxy, C₁–C₆-alkylamino,di-(C₁–C₆-alkyl)amino, C₁–C₁₀-alkoxy, C₁–C₁₀-alkylthio,C₁–C₁₀-alkoxy-C₁–C₁₀-alkoxy, C₁–C₁₀-haloalkoxy, C₁–C₁₀-haloalkylthio,and C₁–C₁₀-haloalkoxy-C₁–C₁₀-alkoxy; or represent C₃–C₁₂-cycloalkyl,C₃–C₇-cycloalkyl-C₁–C₄-alkyl, aryl, aryl-C₁–C₄-alkyl, saturated orunsaturated 5- to 10-membered heterocyclyl or heterocyclyl-C₁–C₄-alkylhaving 1 to 4 heteroatoms, containing 0 to 4 nitrogen atoms, 0 to 2non-adjacent oxygen atoms, and/or 0 to 2 non-adjacent sulphur atoms,each of which is optionally substituted from one to four times byidentical or different substituents selected from the group consistingof fluorine, chlorine, bromine, C₁–C₆-alkyl, C₁–C₆-alkoxy,C₁–C₆-alkylthio, C₁–C₆-haloalkyl, C₁–C₆-haloalkoxy, C₁–C₆-haloalkylthio,C₁–C₆-alkylcarbonyl, and C₁–C₆-alkoxycarbonyl, or R⁶ and R⁷ togetherrepresent C₂–C₄-alkylene optionally substituted from one to four timesby C₁–C₄-alkyl, or R⁷ and R⁸, together with the nitrogen atom to whichthey are attached, represent a saturated or unsaturated 5- to10-membered heterocycle that optionally contains a further heteroatomgroup selected from the series —O—, —S—, or —NR⁹— and that is optionallysubstituted from one to four times by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₆-alkylthio, C₁–C₆-haloalkyl,C₁–C₆-haloalkoxy, and C₁–C₆-haloalkylthio, and R⁹ represents hydrogen,C₁–C₆-alkyl or C₂–C₆-alkenyl.
 3. A Δ¹-pyrroline of formula (I) accordingto claim 2 in which A represents phenylene, Y represents O or S, and Xrepresents O, S, or NR⁸.
 4. A Δ¹-pyrroline of formula (I) according toclaim 2 in which R⁷ and R⁸ independently of one another representtetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl,thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl,pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl,thiazolyl, benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl,pyridazyl, pyrazinyl, piperidinyl, morpholinyl, thiomorpholinyl,triazinyl, triazolyl, quinolinyl, or isoquinolinyl, each of which isoptionally substituted from one to four times by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, C₁–C₆-alkyl, C₁–C₆-alkoxy, C₁–C₆-alkylthio, C₁–C₆-haloalkyl,C₁–C₆-haloalkoxy, C₁–C₆-haloalkylthio, C₁–C₆-alkylcarbonyl, andC₁–C₆-alkoxycarbonyl.
 5. A Δ¹-pyrroline of formula (I) according toclaim 1 in which R¹ represents fluorine, chlorine, or methyl, R²represents hydrogen, fluorine, or chlorine, R³ represents—N(R⁶)—C(═Y)—X—R⁷, A represents phenylene that is optionally substitutedonce or twice by identical or different substituents R⁵, Y represents Oor S, X represents O, S, or NR⁸, R⁴ and R⁵ independently of one anotherrepresent fluorine, chlorine, C₁–C₄-alkyl, C₁–C₄-alkoxy, orC₁–C₄-alkylthio; or C₁–C₄-haloalkyl, C₁–C₄-haloalkoxy, orC₁–C₄-haloalkylthio having in each case 1 to 9 fluorine, chlorine,and/or bromine atoms, m represents 0, 1, or 2, R⁶ represents hydrogen orC₁–C₄-alkyl, R⁷ and R⁸ independently of one another represent hydrogen;represent C₁–C₁₆-alkyl or C₂–C₁₆-alkenyl, each of which is optionallysubstituted one or more times by identical or different substituentsselected from the group consisting of fluorine, chlorine, bromine,C₁–C₄-alkylcarbonyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylamino,di-(C₁–C₄-alkyl)amino, C₁–C₁₀-alkoxy, C₁–C₁₀-alkylthio,C₁–C₁₀-alkoxy-C₁–C₆-alkoxy, C₁–C₁₀-haloalkoxy, C₁–C₁₀-haloalkylthio, andC₁–C₁₀-haloalkoxy-C₁–C₆-alkoxy having in each case 1 to 21 fluorine,chlorine, and/or bromine atoms; or represent C₃–C₁₀-cycloalkyl,C₃–C₆-cycloalkyl-C₁–C₄-alkyl, phenyl, benzyl, phenylethyl, tetrazolyl,furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl,benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl,oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl,benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl,pyrazinyl, piperidinyl, morpholinyl, thiomorpholinyl, triazinyl,triazolyl, quinolinyl, or isoquinolinyl, each of which is optionallysubstituted from one to three times by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkyl,C₁–C₄-haloalkoxy, C₁–C₄-haloalkylthio having in each case 1 to 9fluorine, chlorine, and/or bromine atoms, C₁–C₄-alkylcarbonyl, andC₁–C₄-alkoxycarbonyl, or R⁶ and R⁷ together represent C₂–C₃-alkyleneoptionally substituted from one to three times by C₁–C₄-alkyl, or R⁷ andR⁸, together with the nitrogen atom to which they are attached,represent a saturated or unsaturated 5- to 7-membered heterocycle thatoptionally contains a further heteroatom group selected from the series—O—, —S—, and —NR⁹— and that is optionally substituted from one to fourtimes by identical or different substituents selected from the groupconsisting of fluorine, chlorine, C₁–C₄-alkyl, C₁–C₄-alkoxy,C₁–C₄-alkylthio, C₁–C₄-haloalkyl, C₁–C₄-haloalkoxy, andC₁–C₄-haloalkylthio having in each case 1 to 9 fluorine, chlorine,and/or bromine atoms, and R⁹ represents hydrogen, C₁–C₄-alkyl orC₂–C₄-alkenyl.
 6. A Δ¹-pyrroline of formula (I) according to claim 5 inwhich R⁷ and R⁸, together with the nitrogen atom to which they areattached, represent piperidino, morpholino, thiomorpholino, piperazino,pyrrolidino, oxazolidino, thiazolidino, 4H-1-oxazinyl, or4H-1-thiazinyl, each of which is optionally substituted from one to fourtimes by identical or different substituents selected from the groupconsisting of fluorine, chlorine, C₁–C₄-alkyl, C₁–C₄-alkoxy,C₁–C₄-alkylthio, C₁–C₄-haloalkyl, C₁–C₄-haloalkoxy, andC₁–C₄-haloalkylthio having in each case 1 to 9 fluorine, chlorine,and/or bromine atoms.
 7. A Δ¹-pyrroline of formula (I) according toclaim 1 in which R¹ represents fluorine or chlorine, R² representshydrogen or fluorine, R³ represents —N(R⁶)—C(═Y)—X—R⁷, A represents1,2-phenylene or 1,4-phenylene, each of which is optionally substitutedonce by R⁵, Y represents O or S, X represents O, S, or NR⁸, R⁴ and R⁵independently of one another represent fluorine, chlorine, methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, methoxy,ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy,methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio,i-butylthio, s-butylthio, t-butylthio, trifluoromethyl, trifluoroethyl,trifluoromethoxy, trifluoroethoxy, trifluoro-methylthio, ortrifluoroethylthio, m represents 0 or 1, R⁶ represents hydrogen, methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, or t-butyl, R⁷ andR⁸ independently of one another represent hydrogen; representC₁–C₁₀-alkyl or C₂–C₁₀-alkenyl, each of which is optionally substitutedone or more times by identical or different substituents selected fromthe group consisting of fluorine, chlorine, bromine,C₁–C₄-alkylcarbonyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylamino,di-(C₁–C₄-alkyl)amino, C₁–C₁₀-alkoxy, C₁–C₈-alkoxy-C₁–C₆-alkoxy,C₁–C₁₀-alkylthio, C₁–C₁₀-haloalkoxy, C₁–C₁₀-haloalkylthio having in eachcase 1 to 21 fluorine, chlorine, and/or bromine atoms, andC₁–C₈-haloalkoxy-C₁–C₆-alkoxy having 1 to 17 fluorine, chlorine, and/orbromine atoms; or represent C₃–C₈-cycloalkyl, cyclopropylmethyl,cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl, cyclopentylethyl,cyclohexylethyl, phenyl, benzyl, phenylethyl, tetrazolyl, furyl,furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl,thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl,benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl,benzothiazolyl, thiazolidinyl, pyridinyl, pyrimidinyl, pyridazyl,pyrazinyl, piperidinyl, morpholinyl, thiomorpholinyl, triazinyl,triazolyl, quinolinyl, or isoquinolinyl, each of which is optionallysubstituted from one to three times by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, C₁–C₄-alkyl, C₁–C₄-alkoxy, C₁–C₄-alkylthio, C₁–C₄-haloalkyl,C₁–C₄-haloalkoxy, C₁–C₄-haloalkylthio having in each case 1 to 9fluorine, chlorine, and/or bromine atoms, C₁–C₄-alkylcarbonyl, andC₁–C₄-alkoxycarbonyl, or R⁶ and R⁷ together represent methylene orethylene, each of which is optionally substituted once or twice byidentical or different methyl, ethyl, n-propyl, or i-propylsubstituents, or R⁷ and R⁸, together with the nitrogen atom to whichthey are attached, represent a 5- to 6-membered heterocycle selectedfrom the series consisting of piperidino, morpholino, thiomorpholino,piperazino, pyrrolidino, oxazolidino, thiazolidino, 4H-1-oxazinyl, and4H-1-thiazinyl, each of which is optionally substituted from one to fourtimes by identical or different substituents selected from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, n-propyl,i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, methoxy, ethoxy,n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy,methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio,i-butylthio, s-butylthio, t-butylthio, C₁–C₄-haloalkyl,C₁–C₄-haloalkoxy, and C₁–C₄-haloalkylthio having in each case 1 to 9fluorine, chlorine, and/or bromine atoms, wherein the piperazino radicalis substituted on the second nitrogen atom by R⁹, and R⁹ representshydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl,t-butyl, vinyl, or allyl.
 8. A Δ¹-pyrroline of formula (I) according toclaim 7 in which R⁷ and R⁸ independently of one another representmethyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl,the isomeric pentyls, and the isomeric hexyls, each of which isoptionally substituted one or more times by identical or differentsubstituents selected from the group consisting of fluorine, chlorine,bromine, C₁–C₄-alkylcarbonyl, C₁–C₄-alkylcarbonyloxy, C₁–C₄-alkylamino,di-(C₁–C₄-alkyl)amino, C₁–C₁₀-alkoxy, C₁–C₈-alkoxy-C₁–C₆-alkoxy,C₁–C₁₀-alkylthio, C₁–C₁₀-haloalkoxy, C₁–C₁₀-haloalkylthio having in eachcase 1 to 21 fluorine, chlorine and/or bromine atoms,C₁–C₈-haloalkoxy-C₁–C₆-alkoxy having 1 to 17 fluorine, chlorine and/orbromine atoms.
 9. A Δ¹-pyrroline of formula (I-1) or (I-2)

in each of which Y represents O or S, X represents O, S, or NR⁸, R¹represents halogen or methyl, R² represents hydrogen or halogen, R⁴ andR⁵ independently of one another represent halogen, alkyl, alkoxy,alkylthio, haloalkyl, haloalkoxy, or haloalkylthio, m represents 0, 1,2, 3, or 4, R⁶ represents hydrogen or alkyl, R⁷ and R⁸ independently ofone another represent hydrogen; represent alkyl or alkenyl, each ofwhich is optionally substituted one or more times by identical ordifferent substituents selected from the group consisting of halogen,alkylcarbonyl, alkylcarbonyloxy, alkylamino, dialkylamino, alkoxy,alkylthio, alkoxyalkoxy, haloalkoxy, haloalkylthio, andhalogenalkoxyalkoxy; or represent cycloalkyl, cycloalkylalkyl, aryl,arylalkyl, or saturated or unsaturated 5- to 10-membered heterocyclyl orheterocyclylalkyl, each of which is optionally substituted one or moretimes by identical or different substitutents selected from the groupconsisting of halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio,haloalkylthio, alkylcarbonyl. and alkoxycarbonyl, or R⁶ and R⁷ togetherrepresent alkylene optionally substituted one or more times by alkyl, orR⁷ and R⁸, together with the nitrogen atom to which they are attached,represent a saturated or unsaturated 5- to 10-membered heterocycle thatoptionally contains a further heteroatom group selected from the series—O—, —S—, and —NR⁹— and that is optionally substituted one or more timesby identical or different substituents selected from the groupconsisting of halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy,and haloalkylthio, and R⁹ represents hydrogen, alkyl, or alkenyl.
 10. AΔ¹-pyrroline of formula (I) according to claim 1 in which A representsphenylene.
 11. A Δ¹-pyrroline of formula (I) according to claim 1 inwhich A represents 1,4-phenylene.
 12. A Δ¹-pyrroline of formula (I)according to claim 1 in which Y represents O.
 13. A Δ¹-pyrroline offormula (I) according to claim 1 in which X represents O or NR⁸.
 14. AΔ¹-pyrroline of formula (I) according to claim 1 in which Y and X eachrepresent O.
 15. A Δ¹-pyrroline of formula (I) according to claim 1 inwhich Y represents O and X represents NR⁸.
 16. A Δ¹-pyrroline of formula(I) according to claim 1 in which R¹ and R² each represent fluorine. 17.A Δ¹-pyrroline of formula (I) according to claim 1 in which R¹represents methyl and R² represents hydrogen.
 18. A Δ¹-pyrroline offormula (I) according to claim 1 in which R¹ represents chlorine and R²represents hydrogen.
 19. A Δ¹-pyrroline of formula (I) according toclaim 1 in which R¹ represents chlorine and R² represents fluorine. 20.A Δ¹-pyrroline of formula (I) according to claim 1 in which R⁶represents hydrogen.
 21. A Δ¹-pyrroline of formula (I-a) having (R)configuration in position 5 of the pyrroline ring

in which R¹ represents halogen or methyl, R² represents hydrogen orhalogen, R³ represents —N(R⁶)—C(═Y)—X—R⁷, A represents arylene that isoptionally substituted from one to four times by identical or differentsubstituents R⁵, Y represents O or S, X represents O, S, or NR⁸, R⁴ andR⁵ independently of one another represent halogen, alkyl, alkoxy,alkylthio, haloalkyl, haloalkoxy, or haloalkylthio, m represents 0, 1,2, 3, or 4, R⁶ represents hydrogen or alkyl, R⁷ and R⁸ independently ofone another represent hydrogen; represent alkyl or alkenyl, each ofwhich is optionally substituted one or more times by identical ordifferent substituents selected from the group consisting of halogen,alkylcarbonyl, alkylcarbonyloxy, alkylamino, dialkylamino, alkoxy,alkylthio, alkoxyalkoxy, haloalkoxy, haloalkylthio, andhalogenalkoxyalkoxy; or represent cycloalkyl, cycloalkylalkyl, aryl,arylalkyl, or saturated or unsaturated 5- to 10-membered heterocyclyl orheterocyclylalkyl, each of which is optionally substituted one or moretimes by identical or different substitutents selected from the groupconsisting of halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio,haloalkylthio, alkylcarbonyl. and alkoxycarbonyl, or R⁶ and R⁷ togetherrepresent alkylene optionally substituted one or more times by alkyl, orR⁷ and R⁸, together with the nitrogen atom to which they are attached,represent a saturated or unsaturated 5- to 10-membered heterocycle thatoptionally contains a further heteroatom group selected from the series—O—, —S—, and —NR⁹— and that is optionally substituted one or more timesby identical or different substituents selected from the groupconsisting of halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy,and haloalkylthio, and R⁹ represents hydrogen, alkyl, or alkenyl.
 22. Aprocess for preparing compounds of formula (I) according to claim 1comprising reacting a Δ¹-pyrroline of formula (II)

in which R¹, R², R⁴, and m have the meanings given for formula (I) inclaim 1, and Z¹ represents chlorine, bromine, iodine, —OSO₂CF₃, or—OSO₂(CF₂)₃CF₃,  in a tandem reaction with a compound of formula (III)

in which A, R⁶, and R⁷ have the meanings given for formula (I) in claim1, Y¹ represents O, X¹ represents O or NR⁸, and E represents chlorine,bromine, iodine, —OSO₂CF₃, or —OSO₂(CF₂)₃CF₃,  in the presence of apalladium catalyst, in the presence of a diboronic ester, optionally inthe presence of an acid binder, and optionally in the presence of adiluent.
 23. A pesticide comprising at least one compound of the formula(I) according to claim 1 and one or more extenders and/or surface-activesubstances.
 24. A method of controlling insects, arachnids, or nematodescomprising causing an effective amount of one or more compounds offormula (I) according to claim 1 to act on said insects, arachnids, ornematodes and/or their habitat.
 25. A process for producing pesticidescomprising mixing one or more compounds of formula (I) according toclaim 1 with one or more extenders and/or surface-active substances.